BR112015026441B1 - improved fullerene derivatives and related materials, methods and devices - Google Patents

Abstract

IMPROVED FULLERENE DERIVATIVES AND RELATED MATERIALS, METHODS AND DEVICES. The present invention relates to improved fullerene derivatives, methods for their synthesis and any educts or intermediates used in such methods, compositions and formulations containing fullerene derivatives, the use of fullerene derivatives, compositions and formulations in or for the preparation of electronic devices (OE) such as, for example, organic photovoltaic devices (OPV) or organic photodetectors (OPD) and OE, OPV and OPD devices comprising these, or being prepared therefrom, derivatives, compositions and formulations of fullerene.

Description

Field of Technique

[001] The present invention relates to improved fullerene derivatives, methods for their synthesis and any educts or intermediates used in such methods, compositions and formulations containing fullerene derivatives, the use of fullerene derivatives, compositions and formulations in, or for the preparation of, organic electronic devices (OE) (Organic Electronic) such as, for example, organic photovoltaic devices (OPV) (Organic Photovoltaic) or organic photodetectors (OPD) (Organic Photodetectors) and to OE, OPV and OPD devices comprising these, or being prepared from them, fullerene derivatives, compositions or formulations.

Background

[002] In recent years, there has been development of organic semiconducting materials (OSC) (Organic Semiconducting) in order to produce more versatile electronic devices at a lower cost. Such materials find application in a wide range of devices or apparatus, including organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), organic photodetectors (OPDs) ), organic photovoltaic cells (OPV), sensors, memory elements and logic circuits to name a few. Organic semiconductor materials are typically present in the electronic device in the form of a thin layer, for example, between 50 and 300 nm thick.

[003] The photosensitive layer in an OPV or OPD device is typically composed of at least two materials, a p-type semiconductor such as a polymer, an oligomer or a defined molecular unit and an n-type semiconductor which is, for example, a derivative of fullerene.

[004] Fullerene derivatives are known in the art. See, for example, Hirsch, Brettreich, Fullerenes: Chemistry and Reactions, Wiley, 2005. See also, for example, E. Voroshazi et al., J. Mater. Chem. 2011, 21, 17345-17352; K.-H. Kim et al., Chem.Mater. 2011, 23, 5090-5095; and X. Meng, ACS Appl. Mater. Interfaces 2012, 4, 5966-5973. See also US 2010/0132782 A1, US2012/0004476 A1, WO 2008/018931 A1, WO 2010/087655 A1 and US 8,217,260, which disclose o-QDM (ortho-quinodimethane) fullerenes.

[005] However, while in recent years many p-type semiconductors, mainly polymers, have been prepared to increase the performance of an OPV device, the development of fullerene derivatives suitable for use as n-type semiconductor in OPV devices has been limited to just a few selected candidates such as PCMB-C60. Also, the physical properties of fullerene derivatives known in the art, such as solubility, light stability, thermal stability, are limiting their use in commercial applications.

[006] There is still a need for fullerene derivatives that are easy to synthesize, especially through methods suitable for mass production, show good structural organization and film-forming properties, exhibit good electronic properties, especially a high charge carrier mobility, good processability, especially high solubility in organic solvents and high light and thermal stability.

[007] It was an object of the present invention to provide defullerene derivatives that provide one or more of the advantageous properties mentioned above. Another aim of the invention was to extend the range of type n OSC materials available to the specialist. Other objects of the present invention are readily apparent to the skilled person from the detailed description that follows.

[008] The present inventors have found that one or more of the above objectives can be achieved by providing fullerene derivatives as claimed below. These fullerene derivatives are based on fullerene o-QDM, which is substituted at both alpha positions for the benzene ring.

[009] Fullerene derivatives as claimed below have been found to demonstrate one or more of the improved properties as described above, especially for use in OPV/OPD applications and are more suitable for use as n-type semiconductor in OE devices compared to derivatives of fullerene as disclosed in the prior art.

[0010] US 5,763,719 and DE 4301458 A1 disclose an o-QDMfullerene of the following Formula

[0011] wherein "F" is a fullerene and R1 to R8 mean an H atom or a substituent selected from a wide variety of meanings. However, there is only explicit written disclosure for fullerenes, and their synthesis, where all from R5 to R9 mean H.

[0012] JP2013-128001 A1 and JP 2011-238847A1 reveal a fullerene o-QDM derivative of the Formula that follows

[0013] wherein "FLN" is a fullerene, Ar1 is an aryl group and R1 to R4 signify an H atom or a substituent selected from a wide variety of meanings. Again, there is only explicit described disclosure for fullerenes, and their synthesis, where all from R1 to R4 mean H.

[0014] S. Lu et al., Org. Letters 2013, reveal a fullerene deo-QDM derivative of the Formula that follows

[0015] wherein R2 is methyl and R1 is, for example, COOCH3 or CN.

[0016] Youjun He et al., J. Mater. Chem. 2012, 22, 13391, reveal fullerene o-QDM derivatives of the following Formulas

[0017] However, fullerene derivatives as claimed hereinafter so far have not been disclosed or suggested in the prior art. summary

[0018] The invention relates to compounds of Formula I, including isomers thereof

[0019] in which

[0020] Cn is a fullerene composed of n carbon atoms, optionally with one or more atoms trapped inside,

[0021] Adduct is a secondary adduct, or a combination of secondary adducts, attached to the Cn fullerene,

[0022] m is the number of secondary adducts attached to the fullereneCn, and is 0, an integer > 1 or a non-integer > 0,

[0023] o is an integer > 1,

[0024] R1 to R8 are independently of one another H, a halogen atom or a carboxyl or hydrocarbyl group having 1 to 50 C atoms or the pair of R5 and R6 and/or the pair of R7 and R8 are covalently linked to form a carbocyclic, heterocyclic, aromatic or heteroaromatic group having 3 to 20 ring atoms which is optionally substituted,

[0025] characterized by the fact that in Formula I at least one of R5 and R7 is different from H and at least one of R6 and R8 is different from H.

[0026] The invention further relates to the use of the compounds of Formula I as electron acceptor semiconductor or n-type.

[0027] The invention further relates to the use of compounds of Formula I as an electron acceptor component or n-type in a semiconductor material, organic electronic device or component of an organic electronic device.

[0028] The invention further relates to a composition comprising one or more selected compounds of Formula I.

[0029] The invention further relates to a composition comprising two or more fullerene derivatives, one or more of which are selected from Formula I.

[0030] The invention further relates to a composition comprising one or more selected compounds of Formula I, preferably as electron acceptor component or n-type, and further comprising one or more semiconductor compounds, which preferably have electron donor and p-type properties .

[0031] The invention further relates to a composition comprising one or more compounds selected from Formula I, and further comprising one or more p-type organic semiconductor compounds, preferably selected from conjugated organic polymers.

[0032] The invention further relates to a composition comprising one or more selected compounds of Formula I and further comprising one or more compounds that are selected from compounds having one or more of a semiconducting property, charge transport, orifice transport, transport of electron, orifice blocking, electron blocking, electrical conduction, photoconduction and light emission.

[0033] The invention further relates to the use of a selected compound of Formula I, or a composition comprising the same, as a semiconductor, charge-carrying, electrically conductive, photoconductive or light-emitting material or in an optical, electro- optical, electronic, electroluminescent or photoluminescent or in a component of such device or in an assembly comprising such device or component.

[0034] The invention further relates to a semiconductor, charge-carrying, electrically conductive, photoconductive or light-emitting material, which comprises a compound selected from Formula I or a composition comprising the same as described above and below.

[0035] The invention further relates to a formulation comprising one or more compounds selected from Formula I, or a composition or material comprising the same as described above and below, and further comprising one or more solvents, preferably selected from organic solvents.

[0036] The invention further relates to an optical, electro-optical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising the same, which is prepared using a formulation as described above and below.

[0037] The invention further relates to an optical, electro-optical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising the same, comprising a selected compound of Formula I, or a composition or a material comprising the same as described above and below.

[0038] Optical, electro-optic, electronic, electroluminescent and photoluminescent devices include, without limitation, organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, photoconductors, photodetectors and thermoelectric device.

[0039] The components of the above devices include, without limitation, charge injection layers, charge transport layers, interlayers, planarizing layers, antistatic films, polymer electrolyte (PEM) membranes (Polymer Electrolyte Membranes), conductive substrates and conductive patterns.

[0040] Assemblies comprising such devices or components include, without limitation, integrated circuits (IC) (Integrated Circuits), radio frequency identification (RFID) markers or safety markers or safety devices containing the same, monitors screen or their backlights, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensing devices, biosensors and biochips.

[0041] In addition, the compounds, mixtures or materials of the present invention can be used as electrode materials in batteries and in components or devices for detection and discrimination of DNA sequences.

[0042] The invention further relates to a bulk heterojunction comprising, or being formed of, a composition comprising one or more selected compounds of Formula I and one or more p-type organic semiconductor compounds that are selected from conjugated organic polymers. The invention further relates to a bulk heterojunction (BHJ) OPV device (Bulk Heterojunction), or an inverted BHJ OPV device, comprising such bulk heterojunction.

Terms and Definitions

[0043] As used herein, any reference to "Formula I" or "Formula I and its subformulas" is understood to be inclusive of any specific subFormula of Formula I as shown hereinafter, including, but not limited to, Formulas I1, I2 , I1a, I2a, I1a1, I1a2, I2a1 and I2a2.

[0044] As used herein, the term "fullerene" shall be understood to mean a compound that is composed of an even number of carbon atoms, which form a cage-like fused ring having a surface comprising six-membered rings and five-membered rings , usually with twelve five-membered rings and the rest six-membered rings, optionally with one or more atoms trapped within. The surface of the fullerene can also contain heteroatoms such as B or N.

As used herein, the term "endohedral fullerene" shall be understood to mean a fullerene with one or more atoms trapped within.

[0046] As used herein, the term "metallofullerene" shall be understood to mean an endohedral fullerene where atoms trapped within are selected from metal atoms.

[0047] As used herein, the term "carbon-based fullerene" shall be understood to mean a fullerene without any atoms trapped within, and where the surface is comprised of carbon atoms only.

[0048] As used herein, the term "polymer" shall be understood to mean a molecule of high relative molecular mass whose structure essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass (Pure Appl. Chem. 1996, 68, 2291). The term "oligomer" shall be understood to mean a molecule of intermediate relative molecular mass whose structure essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass (Pure Appl. Chem., 1996, 68, 2291 ). In a preferred meaning as used in the present invention a polymer will be understood to mean a compound having > 1, i.e. at least 2 repeating units, preferably > 5 repeating units, and an oligomer will be understood to mean a compound having > 1 and < 10, preferably < 5, repeat units.

[0049] Further, as used herein, the term "polymer" shall be understood to mean a molecule comprising a main structure (also referred to as "main chain") of one or more distinct types of repeating units (the smallest constitutional unit of the molecule) and is inclusive of the generally known terms "oligomer", "copolymer", "homopolymer" and the like. Furthermore, it will be understood that the term polymer is inclusive of, in addition to the polymer itself, residues of initiators, catalysts and other elements participating in the synthesis of such polymer, where such residues are understood as not being covalently incorporated into it. In addition, such residues and other elements, while normally removed during post-polymerization purification processes, are typically mixed or blended with the polymer in such a way that they generally remain with the polymer when it is transferred between vessels or between solvents or dispersing media.

[0050] As used herein, in a Formula showing a polymer or a repeating unit, an asterisk (*) will be understood to mean a chemical bond to an adjacent unit or end group in the polymer backbone. In a ring, such as, for example, a benzene or thiophene ring, an asterisk (*) will be understood to mean a C atom that is fused to an adjacent ring.

[0051] As used herein, the terms "repeating unit" and "monomeric unit" are used interchangeably and shall be understood to mean the Constitutional Repeating Unit (CRU), which is the smallest constitutional unit whose repetition constitutes a regular macromolecule, a regular oligomer molecule, a regular block or a regular chain (Pure Appl. Chem. 1996, 68, 2291). As used further herein, the term "unit" will be understood to mean a structural unit which may be a repeating unit alone or may together with other units form a constitutionally repeating unit.

[0052] As used herein, a "terminal group" will be understood to mean a group that terminates the backbone of a polymer. The expression "terminal on the mainframe" will be understood to mean a divalent unit or repeating unit which is linked on one side to such a terminal group and on the other side to another repeating unit. Such end groups include endcap groups, or reactive groups that are attached to a monomer forming the polymer backbone that did not participate in the polymerization reaction such as, for example, a group having the meaning of R5 or R6 as defined below.

[0053] As used herein, the term "end capping group" will be understood to mean a group that is attached to, or substituting for, an end group of the polymer backbone. The end capping group can be introduced into the polymer through an end capping process. End capping can be carried out, for example, by reacting the end groups of the polymer backbone with a monofunctional compound ("end capper") such as, for example, an alkyl or aryl halide, an alkyl- or arylstannane or a alkyl or arylboronate. The end cap can be added, for example, after the polymerization reaction. Alternatively, the end cap can be added in situ to the reaction mixture before or during the polymerization reaction. In situ addition of an end cap can also be used to terminate the polymerization reaction and then control the molecular weight of the forming polymer. Typical end cap groups are, for example, H, phenyl and lower alkyl.

As used herein, the term "small molecule" shall be understood to mean a monomeric compound which typically does not contain a reactive group through which it can be reacted to form a polymer, and which is designed to be used in monomeric form. In contrast thereto, the term "monomer" unless otherwise stated will be understood to mean a monomeric compound that bears one or more reactive functional groups through which it can be reacted to form a polymer.

As used herein, the terms "donor" or "donation" and "acceptor" or "accepting" will be understood to mean an electron donor or electron acceptor, respectively. "Electron donor" will be understood to mean a chemical entity that donates electrons to another compound or another group of atoms of a compound. "Electron acceptor" shall be understood to mean a chemical entity that accepts electrons transferred to it from another compound or another group of atoms of a compound. See also International Union of Pure and Applied Chemistry, Compendium of Chemical Technology, Gold Book, Version 2.3.2, August 19, 2012, pages 477 and 480.

[0056] As used herein, the term "n-type" or "n-type semiconductor" shall be understood to mean an extrinsic semiconductor where the conduction electron density is in excess of the mobile orifice density and the term "p-type" or "type semiconductor p" will be understood to mean an extrinsic semiconductor where moving orifice density is in excess of conduction electron density (see also J. Thewlis, Concise Dictionary of Physics, Pergamon Press, Oxford, 1973).

[0057] As used herein, the term "leaving group" shall be understood to mean an atom or group (which may be charged or uncharged) that separates from an atom where it is considered to be the residual or main part of the molecule participating in a reaction specified (see also Pure Appl. Chem., 1994, 66, 1134).

[0058] As used herein, the term "conjugate" shall be understood to mean a compound (eg a polymer) which contains mainly C atoms with sp2 hybridization (or optionally also sp hybridization) and where these C atoms may also be replaced by heteroatoms. In the simplest case this is, for example, a compound with alternating single or double (or triple) C-C bonds, but it is also inclusive of compounds with aromatic units such as, for example, 1,4-phenylene. The term "mainly" in this relationship shall be understood to mean that a compound with naturally occurring defects (spontaneously), or with defects included through design, which may lead to conjugation disruption, is still considered a conjugated compound.

[0059] As used herein, unless otherwise stated, molecular weight is given as the number average molecular weight Mn or weight average molecular weight Mw, which is determined by gel permeation chromatography (GPC) against polystyrene standards in eluent solvents such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene or 1,2,4-trichlorobenzene. Unless otherwise stated, 1,2,4-trichlorobenzene is used as a solvent. The degree of polymerization, also referred to as the total number of repeating units, n, will be understood to mean the average numerical degree of polymerization given as n = Mn/Mu, where Mn is the average numerical molecular weight and Mu is the molecular weight of the unit. single repeat, see JMG Cowie, Polymers: Chemistry & Physics of Modern Materials, Blackie, Glasgow, 1991.

As used herein, the term "carbyl group" shall be understood to mean any monovalent or multivalent organic moiety which comprises at least one carbon atom or without any non-carbon atoms (such as, for example, -C=C-) or optionally combined with at least one non-carbon atom such as B, N, O, S, P, Si, Se, As, Te or Ge (e.g., carbonyl, etc.).

As used herein, the term "hydrocarbyl group" shall be understood to mean a carboxyl group which does not additionally contain one or more H atoms and optionally contains one or more heteroatoms such as, for example, B, N, O, S, P , Si, Se, As, Te or Ge.

As used herein, the term "heteroatom" shall be understood to mean an atom in an organic compound which is not an H or C atom and preferably shall be understood to mean B, N, O, S, P, Si, Se, As, You or Ge.

[0063] A carboxyl or hydrocarbyl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic and may include spiro connected and/or fused rings.

Preferred carboxy and hydrocarbyl groups include alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 25, more preferably 1 to 18 C atoms, still optionally aryl or substituted aryloxy having 6 to 40, preferably 6 to 25 atoms, further alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy, each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, where all such groups actually contain one or more heteroatoms, preferably selected from B, N, O, S, P, Si, Se, As, Te and Ge.

Additional preferred carboxy and hydrocarbyl groups include, for example: a C1-C40 alkyl group, a C1-C40 fluoroalkyl group, a C1-C40 alkoxy group or an oxaalkyl group, a C2-C40 alkenyl group, a C2-group C40 alkynyl, a C3-C40 allyl group, a C4-C40 alkyldienyl group, a C4-C40 polyenyl group, a C2-C40 ketone group, a C2-C40 ester group, a C6-C18 aryl group, a C6-C40 group alkylaryl, a C6-C40 arylalkyl group, a C4-C40 cycloalkyl group, a C4-C40 cycloalkenyl group, and the like. Preferred among the above groups are a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C3-C20 allyl group, a C4-C20 alkyldienyl group, a group C2-C20 ketone, a C2-C20 ester group, a C6-C12 aryl group and a C4-C20 polyenyl group, respectively.

Also included are combinations of groups having carbon atoms and groups having heteroatoms, such as, for example, an alkynyl group, preferably ethynyl, which is substituted with a silyl group, preferably a trialkylsilyl group.

[0067] The carboxyl or hydrocarbyl group can be an acyclic group or a cyclic group. Where the carboxyl or hydrocarbyl group is an acyclic group, it can be straight chain or branched. Where the carboxyl or hydrocarbyl group is a cyclic group, it can be a non-aromatic carbocyclic or heterocyclic group or an aryl or heteroaryl group.

[0068] A non-aromatic carbocyclic group as noted above and below is saturated or unsaturated and preferably has 4 to 30 ring C atoms. A non-aromatic heterocyclic group as referred to above and below preferably has 4 to 30 ring C atoms, where one or more of the ring C atoms are optionally substituted by a heteroatom, preferably selected from N, O, S, Si and Se or by an -S(O)- or -S(O) 2 group. Non-aromatic carbo- and heterocyclic groups are mono- or polycyclic, may also contain fused rings, preferably contain 1, 2, 3 or 4 fused or unfused rings and are optionally substituted with one or more L groups, where

[0069] L is selected from halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR0R00, -C(=O)X0, -C(=O)R0 , -NH2, -NR0R00, -SH, -SR0, -SO3H,

-SO2R0, -OH, -NO2, -CF3, -SF5, silyl or carboxyl or hydrocarbyl optionally substituted with 1 to 40 C atoms which is optionally substituted and optionally comprises one or more heteroatoms, and is preferably alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy with 1 to 20 carbon atoms which is optionally fluorinated, X0 is halogen, preferably F, Cl or Br and R0, R00 have the meanings given above and below and preferably mean H or alkyl with 1 to 12 C atoms.

[0071] L preferred substituents are selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl and fluoroalkoxy having 1 to 12 C atoms or alkenyl or alkynyl having 2 to 12 C atoms.

Preferred non-aromatic carbocyclic or heterocyclic groups are tetrahydrofuran, indane, pyran, pyrrolidine, piperidine, cyclopentane, cyclohexane, cycloheptane, cyclopentanone, cyclohexanone, dihydrofuran-2-one, tetrahydropyran-2-one and oxepan-2-one.

[0073] An aryl group as referred to above and below, preferably 4 to 30 ring C atoms, is mono- or polycyclic and may also contain fused rings, preferably contains 1, 2, 3 or 4 fused or unfused rings, and is optionally substituted with one or more L groups as defined above.

[0074] A heteroaryl group as referred to above and below is preferably 4 to 30 ring C atoms, where one or more of the ring C atoms are replaced by a heteroatom, preferably selected from N, O, S, Si and Se, it is mono- or polycyclic and may also contain fused rings, preferably contains 1, 2, 3 or 4 fused or unfused rings and is optionally substituted with one or more L groups as defined above.

[0075] As used herein, "arylene" will be understood to mean a divalent aryl group and "heteroarylene" will be understood to mean a divalent heteroaryl group, including all preferred meanings of aryl and heteroaryl as given above and below.

[0076] Preferred aryl and heteroaryl groups are phenyl where, further, one or more CH groups may be substituted by N, naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazol, all of which may be unsubstituted, mono- or polysubstituted with L as defined above. More preferred rings are selected from pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2 or 3 pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene , preferably 2-thiophene, selenophene, preferably 2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2-b]furan, furo[2,3-b ] furan, seleno[3,2-b]selenophen, seleno[2,3-b]selenophen, thieno[3,2-b]selenophen, thieno[3,2-b]furan, indole, isoindole, benzo[b ]furan, benzo[b]thiophene, benzo[1,2-b;4,5-b']dithiophene, benzo[2,1-b;3,4-b']dithiophene, quinol, 2-methylquinol, isoquinol , quinoxaline, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benzoxazole, benzothiadiazole, 4H-cyclopenta[2,1-b;3,4-b']dithiophene, 7H-3,4-dithia-7- sila-cyclopenta[a]pentalene, all may be unsubstituted, mono- or polysubstituted with L as defined above. Additional examples of aryl and heteroaryl groups are those selected from the groups shown hereafter.

[0077] An alkyl group or an alkoxy group, ie where the terminal CH2 group is replaced by -O-, can be straight chain or branched. It is preferably straight chain, has 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms and then is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl or hexadecyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, dodecoxy or hexadecoxy, furthermore methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, tridecoxy, for example, tetradecoxy.

[0078] An alkenyl group, that is, where one or more CH2 groups are replaced by -CH=CH-, can be straight chain or branched. It is preferably straight chain, has 2 to 10 C atoms and thus is preferably vinyl, prop-1- or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1- , 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6 -, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.

Especially preferred alkenyl groups are C2-C7-1E-alkenyl, C4-C7-3E-alkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2- C7-1E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl. Examples for particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4 -pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C atoms are generally preferred.

[0080] An oxaalkyl group, ie where a CH2 group is substituted by -O-, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxapentyl, 2-, 3-, 4-, 5- , 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for example.

[0081] In an alkyl group where a CH2 group is replaced by -O- and a CH2 group is replaced by -C(O)-, these radicals are preferably neighbors. In this way these radicals together form a carbonyloxy group -C(O)-O or an oxycarbonyl group -O-C(O)-. Preferably this group is straight chain and has 2 to 6 C atoms. It is then preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxy 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl,propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)propoxyethyl) 2-(ethoxycarbonyl)propoxyethyl) , 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)butyl.

[0082] An alkyl group where two or more CH2 groups are replaced by -O- and/or -C(O)O- can be straight chain or branched. It is preferably straight chain and has 3 to 12 C atoms. Thus, it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4.4 -bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8.8-bis-carboxy-octyl, 9.9 -bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4 ,4-bis(methoxycarbonyl)butyl, 5,5-bis(methoxycarbonyl)pentyl, 6,6-bis(methoxycarbonyl)hexyl, 7,7-bis(methoxycarbonyl)heptyl, 8.8 -bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl) -butyl, 5,5-bis-(ethoxycarbonyl)hexyl.

[0083] A thioalkyl group, ie where a CH2 group is substituted by -S-, is preferably straight chain thiomethyl (-SCH3), 1-thioethyl (-SCH2CH3), 1-thiopropyl (= -SCH2CH2CH3), 1- (thiobutyl), 1-(thiopentyl), 1-(thiohexial), 1-(thioeptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1- (thiododecyl), where preferably the CH2 group adjacent to the sp2 hybridized vinyl carbon atom is substituted.

[0084] A fluoroalkyl group is perfluoroalkyl CIF2i+1, where i is an integer of from 1 to 15, in particular CF3, C2F5, C3F7, C4F9, C5F11, C6F13, C7F15 or C8F17, more preferably C6F3, or partially fluorinated alkyl with 1 to 15 C atoms, in particular 1,1-difluoroalkyl, all are straight or branched.

[0085] Alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, carbonyl and carbonyloxy groups can be achiral or chiral groups. Particularly preferred chiral groups are 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-propylpentyl , in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 2-butyloctoxy, 2-hexyldekoxy, 2-octyldodekoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa -3-methylbutyl, 3-oxa-4-methyl-pentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxy-octoxy, 6-methyloctoxy 2 -chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1 - butoxypropyl-2-oxy, 2-fluoroethyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy, for example. Most preferred are 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro -2-octyl and 1,1,1-trifluoro-2-octyloxy.

Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3methylbutyl), tert-butyl, isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.

[0087] In a preferred embodiment, the alkyl groups are independently selected from primary, secondary or tertiary alkyl or alkoxy having 1 to 30 C atoms, where one or more H atoms are optionally substituted by F or aryl, aryloxy, heteroaryl or heteroaryloxy which is optionally alkylated or alkoxylated and has 4 to 30 ring atoms. More preferred groups of this type are selected from the group consisting of the Formulas which follow.

[0088] where "ALK" means alkyl or alkoxy optionally fluorinated, preferably linear, with 1 to 20, preferably 1 to 12, C atoms, in the case of tertiary groups more preferably 1 to 9 C atoms, and the dotted line means the bond to the ring to which these groups were attached. Especially preferred among these groups are those where ALK subgroups are identical.

As used herein, "halogen" includes F, Cl, Br or I, preferably F, Cl or Br.

[0090] As used herein, -CO-, -C(=O)- and -C(O)- will be understood to mean a carbonyl group, that is, a group having the structure

[0091] Above and below, Y1 and Y2 are independently one of the other H, F, Cl or CN.

[0092] Above and below, R0 and R00 are independently another H or an optionally substituted carboxyl or hydrocarbyl group having 1 to 40 C atoms and mean preferably H or alkyl having 1 to 12 C atoms.

Detailed Description

[0093] The compounds of Formula I are easy to synthesize, especially through methods suitable for mass production, and exhibit advantageous properties, for example, good structural organization and film-forming properties, good electronic properties, especially vehicle mobility of high load, good processability, especially high solubility in organic solvents and high light and thermal stability.

[0094] The compounds of Formula I are especially suitable as an electron acceptor or n-type semiconductor, especially in semiconductor materials containing both donor and acceptor components, and for the preparation of a mixture of p-type and n-type semiconductors that are suitable for use in OPV BHJ devices and OPD devices.

[0095] For application in OPV and OPD, compounds of Formula I, or a mixture comprising two or more fullerene derivatives, one or more of which are selected from Formula I, are mixed with an added p-type semiconductor such as a polymer, an oligomer or molecular unit defined to form the active layer in the OPV/OPD device (also referred to as the "photoactive layer").

[0096] The OPV/OPD device is generally still composed of a first electrode, transparent or semi-transparent, typically provided on a transparent or semi-transparent substrate, on one side of the active layer, and a second metallic or semi-transparent electrode on the other side of the active layer .

[0097] Additional interfacial layer(s) acting as an orifice blocking layer, orifice transport layer, electron blocking layer and/or electron transport layer, typically comprising a metal oxide (e.g., ZnOx, TiOx, ZTO, MoOx, NiOx), a salt (example: LiF, NaF), a conjugated polymer electrolyte (eg: PEDOT:PSS or PFN), a conjugated polymer (eg: PTAA) or an organic compound (eg: NPB, Alq3, TPD) can be inserted between the active layer and an electrode.

[0098] The compounds of Formula I demonstrate the following improved properties compared to the previously disclosed fullerene derivatives for application in OPV/OPD:

[0099] Compared to the fullerene derivatives of the present invention, the fullerene derivatives reported in the prior art, for example, in US 2010/0132782 A1, US 2012/0004476 A1, WO 2008/018931 A1, WO 2010/087655 A1 and US 8,217,260, have low solubility in solvents commonly used to prepare OPV devices.

The substituents R5 to R8 which can each have more than one solubilization group allow for greater fullerene solubility in non-halogenated solvents due to the increased number of solubilization groups.

[00101] Additional adjustment of the electronic energies (HOMO/LUMO levels), through the careful selection of electron acceptance and/or donation unit(s) in the R1 positions of R8, reduces the energy loss in the electron transfer process between the fullerene derivative and a p-type material (eg a polymer, oligomer or defined molecular unit) when used in the active layer of an OPV or OPD device.

[00102] Further adjustment of the electronic energies (HOMO/LUMO levels), through careful selection of electron accepting and/or donating unit(s) at positions R1 to R8, increases the open circuit potential (Voc).

[00103] If R5 or R7 and R6 or R8 are an alkyl chain, the solubility of the fullerene is greatly increased while maintaining the HOMO position similar to the equivalent unsubstituted derivatives (R5 to R8 = H) thereby increasing the open circuit potential ( You) of the device compared to similar device prepared using PCBM.

[00104] If R5 or R7 and R6 or R8 represent the same chemical entity, the resulting fullerene derivatives have a high degree of symmetry, thereby increasing the likelihood of improving the solid state organization of the compound while maintaining sufficient solubility in non-solvents. halogenated.

[00105] In the compounds of Formula I, and their subformulas as defined below, the groups R, R1-R8, are adapted to be structurally distinct and provide useful properties. In addition, adduct groups can provide structural distinction and useful properties, when present. The m value can be, for example, 0, 1, 2 or more for purified compounds. The m value can also be a non-integer such as, for example, 0.5 or 1.5, when mixtures of compounds are present.

[00106] The fullerene Cn in Formula I and its subformulas can be composed of any number n of carbon atoms. Preferably, the number n of carbon atoms of which the fullerene n is composed is 60, 70, 76, 78, 82, 84, 90, 94 or 96, more preferably 60 or 70.

[00107] In a preferred embodiment of the present invention, n in Formula I and its subformulas is 60.

[00108] In another preferred embodiment of the present invention, n in Formula I and its subformulas is 70.

[00109] The Cn fullerene in Formula I and its subFormula is preferably selected from carbon-based fullerene, endohedral fullerene, or mixtures thereof, more preferably from carbon-based fullerene.

[00110] Suitable and preferred carbon-based fullerenes include, without limitation, (C60-Ih)[5,6]fullerene, (C70-D5h)[5,6]fullerene, (C76-D2*) [5,6] fullerene, (C84-D2*)[5,6]fulerene, (C84-D2d)[5,6]fullerene, or a mixture of two or more of the above-mentioned carbon-based fullerenes.

[00111] Endohedral fullerenes are preferably metallofulerenes. Suitable and preferred metallofulerenes include, without limitation, La&C60, La&C82, I&C82, Sc3N&C80, I3N&C80, Sc3C2&C80 or a mixture of two or more of the above-mentioned metallofullerenes.

[00112] In the Formula I fullerene derivatives and their subformulas, the adducts can be attached with any connectivity. Adducts are preferably attached to different carbon atoms in the fullerene; more preferably to two different but adjacent carbon atoms in the fullerene; more preferably to two adjacent different five-membered ring-bonding carbon atoms in the fullerene.

[00113] The Cn fullerene in Formula I and its subformulas is preferably substituted on one bond [6.6] and/or [5.6], preferably substituted on at least one bond [6,6].

[00114] The compounds of Formula I and its subformulas may, in addition to the primary adduct(s) of the structure that follows as shown in Formula I,

[00115] contain any number m of secondary adducts attached to the Cn fullerene, which are called "Adducts" in Formula I and its subformulas.

[00116] The secondary adduct can be any possible adduct or combination of adducts, including o-quinonedimethane analogues, with any connectivity to the fullerene. An example of an adduct is the adduct found in PCBM, where the adduct can be represented by =C(R31)(R32), where R31 is an optionally substituted phenyl group and R32 is -(CH2)COOCH3. R31 can be phenyl and n can be 3.

[00117] In the compounds of Formula I and its subformulas, any adducts may be connected to each other in any combination in the finished product or during synthesis, to facilitate preferred properties in the finished product.

[00118] In the compounds of Formula I and its subformulas, the number: m of secondary adducts attached to the fullerene Cn is 0, an integer > or a non-integer > 0 such as 0.5 or 1.5 is preferably 0, 1, 2 or 3, each preferably 0, 1 or 2.

[00119] In a preferred embodiment of the present invention, m in Formula I and its subformulas is 0.

[00120] In another preferred embodiment, the compound of Formula I and its subformulas is free of any secondary fullerene ortho-quinodimethane adduct including the adduct shown in Formula I.

[00121] In another preferred embodiment of the present invention, m in Formula I and its subformulas is 1, 2 or 3.

em que[00122] The secondary adduct, called "Adduct" in the Formula and its subformulas, is preferably selected from the Formula that follows

on what

[00123] RS1, RS2, RS3, RS4 and RS5 independently of one another mean H, halogen or CN or have one of the meanings of R1 as given above or one of the meanings of ArS1, and

[00124] ArS1 and ArS2 independently of one another mean an aryl or heteroaryl group with 5 to 20, preferably 5 to 15, ring atoms, which is mono- or polycyclic, and which is substituted by one or more identical or different RS substituents, Where

[00125] RS means halogen, preferably F, or a straight, branched or cyclic alkyl moiety having 1 to 30, preferably 4 to 20, more preferably 5 to 15, C atoms, where one or more CH2 groups are optionally substituted by -O-, -S-, -C(O)-, -C(S)-, -C(O)-O-, -OC(O)-, -S(O)2-, -NR0-, -SiR0R00-, -CF2- and R0 and R00 have one of the meanings given above and below, and preferably means H or alkyl having 1 or 12 C atoms.

[00126] In another preferred embodiment of the present invention, m in the Formula and its subformulas is 1, 2 or 3 and the Adduct is selected from Formulas S1 to S9 as defined above.

[00127] [0104] R1 to R8 in Formula I and its subformulas preferably mean H, halogen or a straight-chain, branched or cyclic alkyl group having 1 to 50 C atoms, where one or more CH2 groups are optionally substituted by -O -, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -S(O)2-, -NR0 -, -SiR0R00-, -CF2-, -CHR0=CR00-, -CY1=CY2- or -C=C- such that O and/or S atoms are not directly bonded to each other, or one or more CH2 or CH3 groups are substituted by a cationic group or an anionic group, and where one or more H atoms are optionally substituted by F, Cl, Br, I or CN, or R1 to R8 mean a non-aromatic carbo- or heterocyclic group which is saturated or unsaturated, or an aryl or heteroaryl group, where each of the cyclic groups mentioned above has 3 to 20, preferably 5 to 15, ring atoms, is mono- or polycyclic, contains fused and/or unfused rings, and is optionally substituted by one or more RS groups, where

[00128] RS has one of the meanings of L as given above and means preferably halogen, more preferably F, or a straight chain, branched or cyclic alkyl moiety having 1 to 30, preferably 4 to 20, more preferably 5 to 15, atoms of C, where one or more CH2 groups are optionally substituted by -O-, -S-, -C(O)-, -C(S)-, -C(O)-O-, -OC(O)- , -S(O)2-, -NR0-, -SiR0R00-, -CF2- and R0 and R00 have one of the meanings given above and below, and preferably denote H or alkyl having 1 to 12 C atoms.

[00129] In Formula I and its subformulas preferably one or more of R1, R2, R3, R4, R5, R6, R7 and R8, more preferably all of R1, R2, R3, R4, R5, R6, R7 and R8, mean H.

[00130] More preferably one or more of R1, R2, R3, R4, R5, R6, R7 and R8 signify halogen, or branched, branched or cyclic alkyl group having 1 to 50, preferably 2 to 50, more preferably 2 to 12, C atoms, where one or more CH2 groups are optionally substituted by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O- , -OC(=O)-, -S(O)2-, -NR0-, -SiR0R00-, -CF2-, -CHR0=CR00-, -CY1=CY2- or -C=C- such that the O and/or S atoms are not directly bonded to each other, one or more CH2 or CH3 groups are optionally substituted by a cationic group or an anionic group, and one or more H atoms are optionally substituted by F, Cl, Br, I or CN, and where R0 and R00 and Y1 and Y2 have one of the meanings given above and below and R0 and R00 preferably denote H or alkyl having 1 to 12 C atoms.

[00131] More preferably one or more of R1, R2, R3, R4, R5, R6, R7 and R8 mean an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy group, all are straight or branched, have 2 to 20 C atoms, more preferably 2 to 12 C atoms, more preferably 2 to 12 C atoms, and are optionally fluorinated.

[00132] More preferably one or more of R1, R2, R3, R4, R5, R6, R7 and R8 mean a non-aromatic carbo- or heterocyclic group or an aryl or heteroaryl group, each of the groups mentioned above having 3 to 20 preferably 5 to 15, ring atoms, being mono- or polycyclic, and optionally being substituted by one or more identical or different RS substituents as defined above.

[00133] In Formula I, preferably R5 and R6 are different from H and R7 and R8 mean H or R7 and R8 are different from H and R5 and R6 mean H.

Preferably those of R5, R6, R7 and R8 which are other than H mean halogen or a straight, branched or cyclic alkyl group having 1 to 50, preferably 2 to 50, more preferably 2 to 25, most preferably 2 to 12, C atoms, where one or more CH2 groups are optionally substituted by -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -S(O)2-, -NR0-, -SiR0R00-, -CF2-, -CHR0=CR00-, -CY1=CY2- or -C=C- such that atoms of O and/or S are not directly bonded to each other, and where one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and where

[00135] where R0 and R00 and Y1 and Y2 have one of the meanings given above and below and R0 and R00 preferably mean H or alkyl with 1 to 12 C atoms.

[00136] In another preferred embodiment, those of R5, R6, R7 and R8 which are other than H are selected from aliphatic groups such as optionally substituted C1-C50 alkyl groups, preferably longer than methyl, including C2-C50 alkyl groups optionally substituted, optionally substituted C2-C25 alkyl groups, and optionally substituted C2-C16 alkyl groups. Examples include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and hexadecyl including straight chain, branched and isomeric alkyl groups.

[00137] In another preferred embodiment, those of R5, R6, R7 and R8 which are different from H mean alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy group, all are straight or branched chain, have 2 to 20 atoms of C, more preferably 2 to 12 C atoms, and are optionally fluorinated.

[00138] In another preferred embodiment one or more of R1, R2, R3, R4, R5, R6, R7 and R8 mean a straight, branched or cyclic alkyl group having 1 to 50, preferably 2 to 50, more preferably 2 to 25, most preferably 2 to 12, C atoms, where one or more CH2 or CH3 groups are replaced by a cationic or anionic group.

[00139] The cationic group is preferably selected from the group consisting of phosphonium, sulphonium, ammonium, uronium, thiouronium, guanidinium or heterocyclic cations such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium.

[00140] Preferred cationic groups are selected from the group consisting of tetra-alkylammonium, tetra-alkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium, where "alkyl" preferably means a straight or branched chain alkyl group with 1 to 12 C atoms.

[00141] Additional preferred cationic groups are selected from the group consisting of the Formulas that follow

[00142] wherein R1', R2', R3' and R4' signify, independently of one another, H, a straight or branched chain alkyl group with 1 to 12 C atoms or a non-aromatic carbo- or heterocyclic group or a aryl or heteroaryl group, each of the groups mentioned above having 3 to 20, preferably 5 to 15, ring atoms, and being substituted by one or more identical or different substituents RS as defined above, or signify a bond to the group R 1 , R 2 , R3, R4, R5, R6, R7 or R8, respectively.

[00143] In the above cationic groups of the above mentioned Formulas any of the groups R1', R2', R3' and R4' (if they replace a CH3 group) can mean a bond to the respective group R1, R2, R3, R4, R5 , R6, R7 or R8 or two neighboring groups R1', R2', R3' or R4' (if they replace a CH2 group) may signify a bond to the respective group R1, R2, R3, R4, R5, R6, R7 or R8.

[00144] The anionic group is preferably selected from the group consisting of borate, imidate, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate, more preferably of phosphate, sulfonate or naphthenate.

[00145] A preferred compound of Formula I is selected from subFormula II

[00146] wherein Cn, "Adduct", m, R5 and R6 have one of the meanings of Formula I or one of the preferred meanings given above, with R5 and R6 being other than H.

[00147] A preferred compound of subFormula l1 is selected from subFormula l1a

[00148] wherein Cn, R5 and R6 have one of the meanings of Formula I or one of the preferred meanings given above, with R5 and R6 being different from H.

[00149] Another preferred embodiment of the present invention relates to compounds of Formula 1 and its subformulas, wherein the pair of R5 or R6 and/or the pair of R7 and R8, preferably only the pair of R7 and R8, are covalently linked to form a carbocyclic, heterocyclic, aromatic or heteroaromatic group having 3 to 20 ring atoms which is optionally substituted.

[00150] Preferably the pair of R7 and R8 is covalently linked to form a cyclic group of the Formula

[00151] where Ars1 is as defined in Formula S3 above.

[00152] More preferably the pair of R7 and R8 is covalently linked to form a cyclic group of the Formula

[00153] wherein R 1-4 has one of the meanings of Formula 1 or one of the preferred meanings given above. These preferred compounds are selected from subFormula 12

wherein Cn, "Adduct", m, R1-4, R5 and R6 have one of the meanings of Formula I or one of the preferred meanings given above, and preferably R5 and R6 are other than H.

[00155] [0124] A preferred compound of subFormula 12 is selected from subFormula 12a

wherein Cn, "Adduct", m, R5 and R6 have one of the meanings of Formula I or one of the preferred meanings given above, and preferably R5and R6 are other than H.

[00157] Additional preferred compounds are those of the sub-formula shown below.

[00158] wherein R5 and R6 independently of one another stand for straight or branched chain alkyl having 1 to 20, preferably 2 to 15, C atoms, and preferably stand for ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.

[00159] The synthesis of the compounds of Formula I and its subformulas can be obtained based on method steps that may be known to the person skilled in the art and described in the literature, but in combination they are new and inventive, as will be further illustrated below.

Especially suitable and preferred synthetic methods of the compounds of Formula I and its subformulas are illustrated in Synthesis Schemes 1-3 shown below.

[00161] [0128] An embodiment provides, for example, a method of manufacturing a Compound according to Formula I comprising

(P-1)[00162] reaction in one or more steps of a precursor P-1 represented by P-1, where R1 to R8 have the meanings given above and below,

(P-1)

(P-2)[00163] with at least one halogenating reagent to form a halogenated intermediate represented by P-2, where Hal means a halogen atom and R1 to R8 have the meanings above and below,

(P-2)

[00164] reaction of intermediate P-2 in one or more steps with a fullerene compound represented by F-1 or F-2:

[00165] (in other words, in F-1, m is zero) and optionally with a secondary adduct compound to form the compound of Formula I.

[00166] These synthetic methods are further illustrated in Synthetic Schemes 1-3 that follow, where for the manufacturing methods illustrated below and above R1-R4 and R5-R8, and the fullerene compound, including Cn and (adduct)m are as defined elsewhere here. The working examples further illustrate the synthetic methods and the nature of the substituents. In one embodiment, as described elsewhere herein, the groups R7 and R8 may be covalently bonded together to form a cyclic group, e.g., a phenyl ring, as illustrated, for example, in Formulas I2 and 12a.

[00167] The precursor compound P-1 can be purchased or made by methods known in the art. Working Example 1.1 below provides an example.

Halogenation reagents (or agents) are known in the art and can include fluorination, chlorination, bromination and iodination reagents (see, for example, March's Advanced Organic Chemistry, 6th Ed., 2007, including pages 954-964). In one embodiment, the halogenating reagent can be a bromination reagent. An example is NBS (N-Bromosuccinimide). The halogenating reagent can be selected based on its ability to selectively halogenate. As used herein, "hal" means "halogen". See Example work below 1.2. For the halogenation reaction, appropriate reaction conditions such as solvent, reaction temperature and purification methods can be used by one skilled in the art. Intermediate compound P-2 can be characterized by methods known in the art.

In a preferred embodiment, the intermediate compound P-2 is directly reacted without purification with the fullerene compound. For example, in some embodiments, purification can be attempted using a chromatographic medium such as an untreated silica gel, but a chromatographic medium such as an untreated silica gel can induce decomposition of the P-2 product. The person skilled in the art can determine whether the chromatographic medium induces decomposition. For example, surface nature, morphology, particle size and pore size can be reviewed. Decomposition can, in some cases, be a function of the surface treatment of the chromatographic medium. Silica gel and other chromatographic media can be surface functionalized as known in the art with, for example, hydrophobic moieties. For example, silica gel can be treated with pyridine. Reverse phase silica gel is known. Untreated silica gel can have a relatively polar surface compared to treated silica to increase the hydrophobicity of the silica gel surface. In one embodiment, the use of untreated silica is avoided in purifying compound P-2 prior to reacting this compound with the fullerene compound. In particular in one embodiment, the intermediate compound P-2 is directly reacted without purification with the fullerene compound. In this modality, solvent can be removed prior to reaction with fullerene. In another particular embodiment, the intermediate compound P-2 is not contacted with untreated silica gel before being reacted with the fullerene compound.

[00170] For the reaction of P-2 with the fullerene compound, appropriate reaction conditions such as solvent, reaction temperature, other reagents such as crown ethers and purification methods can be used by one skilled in the art. Working Examples 1.3 and 2.1 provide preferred modalities. The fullerene compound can either have an adduct as shown in Formula I or it can be free of an adduct as shown in Formula I (m=0). If the latter, an additional reaction may be carried out if desired to form the adduct substituent(s) on the fullerene. These two courses of reaction are illustrated in Scheme 1. Schemes 2 and 3 represent preferred modalities. In them R1 to R4 have the meanings given above and below and R9, R10, R11, R12 have the meanings given for R5, R6, R7, R8, respectively.

Novel methods of preparing fullerene derivatives as described above and below, and the educts and/or intermediates used therein, are another aspect of the invention.

[00172] The compounds of Formula I and its subformulas can also be used in mixtures, for example, together with other monomeric compounds, or polymers, having one or more of the properties of semiconducting, charge transport, orifice transport, electron transport , orifice blocking, electron blocking, electrical conduction, photoconduction and light emission.

[00173] Accordingly, another aspect of the invention relates to a composition (hereinafter referred to as "fullerene composition") comprising one or more selected fullerene derivatives of Formula I and its subformulas or preferred embodiments as described above and below (hereinafter referred to only as "fulerene derivative of the present invention"), and one or more additional compounds, preferably having one or more of the properties of semiconducting, charge transport, orifice transport, electron transport, orifice blocking, electron blocking, electrical conduction, photoconduction and light emission.

[00174] In a preferred embodiment, the composition consists essentially of, or consists of, one or more components including the compounds of Formula I and its subformulas.

[00175] Additional compounds in the fullerene composition may be selected, for example, from fullerene derivatives other than those of the present invention, or from conjugated organic polymers.

[00176] A preferred embodiment of the present invention relates to a fullerene composition comprising one or more fullerene derivatives, at least one of which is a fullerene derivative of the present invention, and further comprising one or more conjugated organic polymers, which are preferably selected from electron donor or p-type semiconductor polymers.

[00177] Such a fullerene composition is especially suitable for use in the photoactive layer of an OPV or OPD device. Preferably the fullerene(s) and polymer(s) are selected such that the fullerene composition forms a bulk heterojunction (BHJ).

[00178] A suitable conjugated organic polymer (hereinafter simply referred to as "polymer") for use in a fullerene composition according to the present invention may be selected from polymers as described in the prior art, for example, in WO/2010 /008672, WO/2010/049323, WO2011/131280, WO/2011/052709, WO/2011/052710, US/2011/0017956, WO/2012/030942 or US/8334456B2.

[00179] A preferred polymer is selected from the group consisting of poly(3-substituted thiophene) and poly(3-substituted selenophene), for example, poly(3-alkyl thiophene) or poly(3-alkyl selenophene), preferably poly( 3-hexyl thiophene) or poly(3-hexyl selenophene).

[00180] An additional preferred polymer comprises one or more repeating units selected from Formulas PIIa and PIIb: -[(Ar1)a-(D)b-(Ar2)c-(Ar3)d]-PIIa-[(Ar1) a-(Ac)b-(Ar2)c-(Ar3)d]-Plb

[00181] in which

[00182] Ac is arylene or heteroaryl with 5 to 3 ring atoms which is optionally substituted by one or more RS groups and preferably has electron acceptor property,

[00183] D is aryl or heteroaryl with 5 to 30 ring atoms which is other than A, is optionally substituted by one or more RS groups and preferably has electron donor property,

[00184] Ar1, Ar2, Ar3 are, at each occurrence identically or differently, and independently of one another, arylene or heteroaryl which is different from A and D, preferably has 5 to 30 ring atoms, and is optionally substituted, preferably by one or more RP groups,

[00185] RP is in each occurrence identically or differentlyF, Br, Cl, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(O)NR0R00, -C(O)X0, -C (O)R0, -C(O)OR0, -NH2, -NR0R00, -SH, -SR0, -SO3H, -SO2R0, -OH, -NO2, -CF3, -SF5, silyl, carboxyl or hydrocarbyl optionally substituted with 1 to 40 C atoms which is optionally substituted and optionally comprises one or more heteroatoms,

[00186] R0 and R00 are independently of one another H or C1-40carbyl or optionally substituted hydrocarbyl and mean preferably H or alkyl having 1 to 12 C atoms,

[00187] X0 is halogen, preferably F, Cl or Br,

[00188] a, b, c are in each occurrence identically or differently 0, 1 or 2,

[00189] d is at each occurrence identically or different 0 or an integer from 1 to 10.

[00190] Preferably the polymer comprises at least one repeating unit of Formula PIIa where b is at least 1. Preferably further the polymer comprises at least one repeating unit of Formula PIIa where b is at least 1 and at least one repeating unit of Formula PIIb where b is at least 1.

[00191] A further preferred polymer comprises, in addition to the units of Formula PIIa and/or PIIb, one or more repeating units selected from monocyclic or polycyclic arylene or heteroarylene groups which are optionally substituted.

Such additional repeating units are preferably selected from Formula PIII-[(Ar1)a-(Ar2)c-(Ar3)d]-PIIIwherein Ar1, Ar2, Ar3, a, c and d are as defined in Formula PIIa.

RP preferably means, at each occurrence identically or differently, H, straight chain, branched or cyclic alkyl having 1 to 30 C atoms, where one or more CH2 groups are optionally substituted by -O-, -S- , -C(O)-, -C(S)-, -C(O)-O-, -O- C(O)-, -NR0-, -SiR0R00-, -CF2-, -CHR0=CR00- , -CY1=CY2- or -C=C- in such a way that O and/or S atoms are not directly bonded to each other, and where one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or means aryl, heteroaryl, aryloxy or heteroaryloxy with 4 to 20 ring atoms which is optionally substituted, preferably by halogen or by one or more of the cyclic alkyl or alkyl groups mentioned above, where R0 and R00 and Y1 and Y2 have one of the meanings given above and below, R0 and R00 preferably mean H or alkyl having 1 to 12 C atoms and Y1 and Y2 preferably mean F, Cl or Br.

[00194] Preferably still the polymer is selected from Formula PIV:

[00195] in which

[00196] A, B, C independently of one another signify a distinct unit of Formula PIIa, PIIb or PIII,

[00197] x is > 0 and < 1,

[00198] y is > 0 and < 1,

[00199] z is > 0 and < 1,

[00200] x+y+z is 1, and

[00201] n1 is an integer of >1.

[00202] Preferably at least one of B or C means a unit of Formula PIIa. More preferably one of B and C means a unit of Formula PIIa and one of B and C means a unit of Formula PIIb.

[00203] A preferred polymer of Formula PIV is selected from the following Formulas* -[(Ar1-D-Ar2)x-(Ar3)i]ni-*PIVa* -[(Ar1-D-Ar2)x-(Ar3 -Ar3)i]ni-* PIVb* -[(Ar1 - D-Ar2)x-(Ar3-Ar3-Ar3)i]n1-* PIVc* -[(Ar1)a-(D)b-(Ar2) c-(Ar3)d]n1-* PIVd* -([(Ar1)a-(D)b-(Ar2)c-(Ar3)d]x-[(Ar1)a-(Ac)b-(Ar2 )c-(Ar3)d]i)n1-* PIVe* -[(D-Ar1-D)x-(Ar2-Ar3)i]n1-* PIVf* -[(D-Ar1-D)x-( Ar2-Ar3-Ar2)i]n1-* PIVg* -[(D)b-(Ar1)a-(D)b-(Ar2)c]n1-* PIVh* -([(D)b-(Ar1 )a-(D)b-(Ar2)c]x-[(Ac)b-(Ar1)a-(Ac)b-(Ar2)d]i)n1-* PIVi* -[(D-Ar1) x-(D-Ar2)i-(D-Ar3)z]n1-* PIVk

[00204] where D, Ar1, Ar2, Ar3, a, b, c and d have in each occurrence identically or differently one of the meanings given in Formula PIIa, Ac has in each occurrence identically or differently one of the meanings given in Formula PIIb ex, y, z and n1 are as defined in Formula PIV, where these polymers may be alternating or random copolymers, and where in Formulas PIVa and PIVe in at least one of the repeating units [(Ar1)a-(D)b-(Ar2) c-(Ar3)d] and in at least one of the repeating units [(Ar1)a-(Ac)b-(Ar2)c-(Ar3)d] b is at least 1 and where in Formulas PIVh and PIVi in at least one of the repeating units [(D)b-(Ar1)a-(D)b-(Ar2)d] and in at least one of the repeating units [(D)b-(Ar1)a-(D) )b-(Ar2)d] b is at least 1.

[00205] In the polymer, the total number of repeating units n1 is preferably from 2 to 10,000. The total number of repeating units n1 is preferably >5, more preferably >10, most preferably >50 and preferably <500, more preferably <1,000, most preferably <2,000, including any combination of the lower and upper limits of n1 mentioned above.

[00206] The polymer may be a homopolymer or copolymer, such as a statistical or random copolymer, alternating copolymer or block copolymer or a combination of those mentioned above.

[00207] Especially preferred is a polymer selected from the following groups:

[00208] - Group A consisting of homopolymers of the D unit or (Ar1-D) or (Ar1-D-Ar2) or (Ar1-D-Ar3) or (D-Ar2-Ar3) or (Ar1-D-Ar2- Ar3) or (D-Ar1-D), ie where all repeating units are identical,

[00209] - Group B consisting of random or alternating copolymers formed by identical units (Ar1-D-Ar2) or (D-Ar1-D) and identical units (Ar3),

[00210] - Group C consisting of random or alternating copolymers formed by identical units (Ar1-D-Ar2) or (D-Ar1-D) and identical units (A1),

[00211] - Group D consisting of random or alternating copolymers formed by identical units (Ar1-D-Ar2) or (D-Ar1-D) and identical units (Ar1-Ac-Ar2) or (Ac-Ar1-Ac),

[00212] where in all these groups D, Ac, Ar1, Ar2 and Ar3 are as defined above and below, in groups A, B and C Ar1, Ar2 and Ar3 are different from a single bond and in the D group one of Ar1 and Ar2 can also mean a single connection.

[00213] [0153] A preferred polymer of Formulas PIV and PIVa aPIVk is selected from Formula PVR21-chain-R22 PV

wherein "chain" means a polymer chain of Formulas PIV or PIVa to PIVk, and R21 and R22 independently of one another have one of the meanings of RS as defined above or independently of one another mean H, F, Br, Cl, I, -CH2Cl, -CHO, -CR'=CR"2, -SiR'R"R"', -SiR'X'X", -SiR'R"X', -SnR'R" R"',

[00215] -BR'R", -B(OR')(OR"), -B(OH)2, -O-SO2-R', -C=CH, -C=C-SiR'3, - ZnX' or an end cap group, X' and X" signify halogen, R', R" and R"' independently of each other have one of the meanings of R0 given in Formula I, and two of R', R" and R"' may also form a ring together with the heteroatom to which they are attached.

Preferred end capping groups R21 and R22 are optionally substituted H, C1-C20 alkyl or C6-C12 aryl or C2-10 heteroaryl, more preferably H or phenyl.

[00217] In the polymer represented by Formulas PIV, PIVa to PIVk, x, y and z mean the mol fraction of A, B and C units, respectively, and n means the degree of polymerization or total number of A, B and C units. Formulas include block copolymers, random or statistical copolymers and alternating copolymers of A, B and C, as well as homopolymers of A for the case when x>0 and y=z=0.

[00218] In the repeating units and polymers of Formulas PIIa, PIIb, PIII, PIV, PIVa-PIVk and PV, preferably D, Ar1, Ar2 and Ar3 are selected from the group consisting of the Formulas that follow

[00219] wherein R11, R12, R13, R14, R15, R16, R17 and R18 independently of one another mean H or have one of the meanings of RP as defined above and below.

[00220] In the repeating units and polymers of Formulas PIIa, PIIb, PIII, PIV, PIVa-PIVk and PV, preferably Ac, Ar1, Ar2 and Ar3 are selected from the group consisting of the following Formulas

[00221] wherein R11, R12, R13, R14, R15 and R16 independently of one another mean H or have one of the meanings of RP as defined above and below.

[00222] The polymer can be prepared, for example, from monomers selected from the following Formulas R23-(Ar1)aD-(Ar2)c-R24 PVIaR23-D-(Ar1)aD-R24 PVIbR23-(Ar1)a- Ac-(Ar2)c-R24 PVIcR23-Ac-(Ar1)a-Ac-R24 PVIdR23-(Ar1)a-(Ar2)c-R24 PVIe

[00223] wherein Ac, D, Ar1, Ar2, a and b have the meanings of Formulas PIIa and PIIb, or one of the preferred meanings as described above and below, and R23 and R24 are preferably, independently of one another, selected from the group consisting of in H, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, -SiMe2F, -SiMeF2, -O-SO2Z1, -B(OZ2)2, -CZ3=C(Z3) 2, -C CH, -C=CSi(Z1)3, -ZnX0 and -Sn(Z4)3, where X0 is halogen, preferably Cl, Br or I, Z1-4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two Z2 groups can also together form a cyclic group.

[00224] Suitable monomers are, for example, selected from the subformulas that follow R23-Ar1-D-Ar2-R24 PVIa1R23-D-R24 PVIa2R23-Ar1-D-R24 PVIa3R23-D-Ar2-R24 PVIa4R23-D-Ar1-D- R24 PVIb1R23-Ar1-Ac-Ar2-R24 PVIc1R23-Ac-R24 PVIc2R23-Ar1-Ac-R24 PVIc3R23-Ac-Ar2-R24 PVIc4R23-Ac-Ar1-Ac-R24 PVId1R23-Ar1-R24 PVIe1R23-Ar1-Ar2-R24 PVIe2

[00225] wherein Ac, D, Ar1, Ar2, a, c, R23 and R24 are as defined in Formulas PVIa-PVId.

[00226] The polymer can be synthesized according to or in analogy to methods that are known to the person skilled in the art and are described in the literature. Other methods of preparation can be obtained from the examples. For example, polymers can generally be prepared through aryl-aryl coupling reactions, such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, C-H activation coupling, Heck coupling, or Buchwald coupling. Suzuki coupling, Stille coupling and Yamamoto coupling are especially preferred. Monomers that are polymerized to form the repeating units of the polymers can be prepared according to methods that are known to the person skilled in the art.

[00227] For example, the polymer can be prepared by coupling one or more monomers selected from the Formulas PVIa-PVId and its subformulas in an aryl-aryl coupling reaction, where R23 and R24 are selected from Cl, Br, I , -B(OZ2)2 and -Sn(Z4)3.

[00228] Preferred aryl-aryl coupling and polymerization methods used in the processes described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, CH activation coupling, Ullmann coupling or coupling Buchwald. Especially preferred are Suzuki coupling, Negishi coupling, Stille coupling and Yamamoto coupling. Suzuki coupling is described, for example, in WO 00/53656A1. Negishi coupling is described, for example, in J. Chem. Soc., Chem. Commun., 1977, 683-684. Yamamoto Coupling is described in, for example, T. Yamamoto et al., Prog. Polym. Sci., 1993, 17, 1153-1205 or WO 2004/022626 A1, and the Stille coupling is described, for example, in Z. Bao et al., J. Am. Chem. Soc., 1995, 117, 12426-12435. For example, when using Yamamoto coupling, monomers having two reactive halide groups are preferably used. When using Suzuki coupling, monomers of Formulas PVIa-PVId and its subformulas having two reactive boronic acid and boronic acid ester groups or two reactive halide groups are preferably used. When using Stille coupling, monomers having two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, monomers having two reactive organozinc groups or two reactive halide groups are preferably used.

[00229] Preferred catalysts, especially for Suzuki, Negishi or Stille coupling, are selected from Pd(0) complexes or Pd(II) salts. Preferred Pd(0) complexes are those carrying at least one phosphine linker such as Pd(Ph3P)4. Another preferred phosphine linker is tris(ortho-tolyl)phosphine, i.e., Pd(o-Tol3P)4. Preferred Pd(0) salts include palladium acetate, i.e., Pd(OAc) 2 . Alternatively the Pd(0) complex can be prepared by mixing a Pd(0) dibenzylideneacetone complex, for example, tris(dibenzylideneacetone)dipalladium(0), dib(dibenzylideneacetone)-palladium(0) or Pd(II) salts ), for example palladium acetate, with a phosphine linker, for example triphenylphosphine, tris(ortho-tolyl)phosphine or tri(tert-butyl)phosphine. Suzuki polymerization is carried out in the presence of a base, for example, sodium carbonate, potassium carbonate, lithium hydroxide, potassium phosphate or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide. Yamamoto polymerization employs a Ni(0) complex, eg bis(1,5-cyclooctadienyl) nickel(0).

[00230] Suzuki and Stille polymerization can be used to prepare homopolymers as well as random, alternating and block random copolymers. Statistical or block copolymers can be prepared, for example, from the above monomers of Formula PVI or its sub-formulas, where one of the reactive groups is halogen and the other reactive group is a boronic acid, a group derived from boronic acid or an alkylstannane. The synthesis of staggered and block statistical copolymers is described in detail, for example, in WO 03/048225 A2 or in WO 2005/014688 A2.

[00231] The concentration of the fullerene derivatives of the present invention, or the fullerene composition, in a formulation according to the present invention, including solvent, is preferably 0.1 to 10% by weight, more preferably 0.5 to 5 % by weight. The concentration of the fullerene derivatives of the present invention in a composition comprising a fullerene derivative and a polymer according to the present invention (i.e. excluding solvents) is preferably from 10 to 90% by weight, more preferably from a from 33% to 80% by weight.

Another aspect of the present invention relates to a formulation comprising one or more fullerene derivatives of the present invention or a fullerene composition as described above and further comprising one or more solvents, preferably selected from organic solvents.

[00233] Such a formulation is preferably used as a vehicle for preparing a semiconductor layer of an OE device, such as an OPV or OPD device, where the fullerene derivative or fullerene composition is, for example, used in the photoactive layer.

Optionally, the formulation further comprises one or more binders to adjust the rheological properties, as described, for example, in WO 2005/055248 A1 .

[00235] The formulations according to the present invention preferably form a solution.

[00236] The solubility of the fullerene compounds of the invention can be substantially increased compared to the solubility of a non-inventive standard compound used as a standard (see working examples below where o-QDM-C60 was used as a standard in o-dichlorobenzene). For example, the solubility of the compound of the invention can be at least 2X, 3X, 4X, 5X, 10X, 15X, 20X or 25X that of the standard. The solubility in a solvent, such as an organic solvent such as, for example, o-dichlorobenzene, may be, for example, at least 10 mg/cm3 or at least 20 mg/cm3 or at least 30 mg/cm3 or at least 40 mg/cm3 or at least 50 mg/cm3 or at least 80 mg/cm3 or at least 100 mg/cm3 or at least 150 mg/cm3. There is no particular upper limit on solubility, but solubility can be, for example, less than 1000 mg/cm3 or less than 500 mg/cm3 or less than 250 mg/cm3. A test to measure solubility is provided in the working examples. The test temperature can be, for example, room temperature or room temperature such as, for example, about 22°C. Other solvents and fullerene compounds can be used in the exemplified test.

[00237] The invention further provides an electronic device comprising a fullerene derivative of the present invention or fullerene composition, or a semiconductor layer comprising the same, as described above and below.

[00238] Especially preferred devices are OFETs, TFTs, ICs, logic circuits, capacitors, RFID markers, OLEDs, OLETs, OPEDs, OPVs, OPDs, solar cells, laser diodes, photoconductors, photodetectors, electrophotographic devices, electrophotographic recording devices , organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarization layers, antistatic films, conductive substrates and conductive patterns.

[00239] Especially preferred electronic devices are OFETs, OLEDs, OPV and OPD devices, in particular volume heterojunction OPV (BHJ) devices and OPD devices. In an OFET, for example, the active semiconductor channel between the drain and the source may comprise the layer of the invention. As another example, in an OLED device, the charge injection layer (orifice or electron) or transport can comprise the layer of the invention.

[00240] For use in OPV and OPD devices, preferably a fullerene composition is used, which contains a p-type semiconductor (electron donor) and an n-type semiconductor (electron acceptor). The p-type semiconductor is, for example, a conjugated polymer having repeating units of Formula PIIa, PIIb or PIII or a polymer of Formula PIV, PV or subformulas thereof, as shown above. The n-type semiconductor is a fullerene derivative of the present invention, or a mixture of two or more fullerene, at least one of which is a fullerene derivative of the present invention.

[00241] More preferably the OPV or OPD device comprises, between the active layer and the first or second electrode, one or more additional buffer layers acting as an orifice transport layer and/or electron blocking layer, which comprises such a material as a metal oxide, such as, for example, ZTO, MoOx, NiOx, a conjugated polymer electrolyte, such as, for example, PEDOT:PSS, a conjugated polymer, such as, for example, polytriarylamine (PTAA), a organic compound such as, for example, N,N'-diphenyl-N,N'-bis(1-naphthyl)(1,1'-biphenyl)-4,4'-diamine (NPB), N,N'- diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD) or alternatively acting as an orifice blocking layer and/or electron transport layer, which comprises a material such as a metal oxide such as, for example, ZnOx, TiOx, a salt such as, for example, LiF, NaF, CsF, a conjugated polymer electrolyte such as, for example, poly[3-( 6-tri-methylammoniohexyl)thiophene], poly(9,9-bi s(2-ethylhexyl)-fluorene]-b-poly[3-(6-trimethylammoniohexyl)thiophene] or poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7- fluorene)-alt-2,7-(9,9-dioctylfluorene)] or an organic compound such as, for example, tris(8-quinolinolate)-aluminium(III) (Alq3), 4,7-dphenyl-1, 10-phenanthroline.

[00242] In a fullerene composition comprising a fullerene derivative and a polymer according to the present invention, the polymer:fulerene derivative ratio is preferably from 5:1 to 1:5 by weight, more preferably from from 1:1 to 1:3 by weight, most preferably 1:1 to 1:2 by weight. A polymeric binder can also be included, from 5 to 95% by weight. Examples of binder include polystyrene (PS), polypropylene (PP) and polymethylmethacrylate (PMMA).

[00243] To produce thin layers in OE devices, such as OPV BHJ devices, a fullerene derivative, fullerene composition or formulation according to the present invention can be deposited by any suitable method. Liquid coating of devices is more desirable than vacuum deposition techniques. Solution deposition methods are especially preferred. The formulations of the present invention allow the use of various liquid coating techniques. Preferred deposition techniques include, without limitation, dip coating, spin coating, inkjet printing, nozzle printing, press printing, screen printing, gravure printing, scalpel coating, roller printing, reverse roller printing , offset lithographic printing, dry offset lithographic printing, flexographic printing, web printing, spray coating, curtain coating, brush coating, slit dye coating or pad printing. For OPV fabrication, area printing methods of devices and modules compatible with flexible substrates are preferred, for example, dye slot coating, spray coating and the like.

[00244] When preparing a suitable solution or formulation containing a composition with a fullerene derivative (as n-type component) and a polymer (as p-type component) according to the present invention, a suitable solvent must be selected in order to ensure total dissolution of the component of both p-type and n-type and take into account the boundary conditions (eg rheological properties) introduced by the chosen printing method.

[00245] Organic solvents are generally used for this purpose. Typical solvents can be aromatic solvents, halogenated solvents or chlorinated solvents, including chlorinated aromatic solvents. Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Examples include, but are not limited to, 1,2,4-trimethylbenzene, 1,2,3,4-tetra-methyl benzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, dekaline, 2, 6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chloro-benzotrifluoride, N,N-dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoranisole, anisole, 2,3- dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoromethylanisole, 2-methylanisole, phenetol, 4-methylanisole, 3-methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, 3-fluorobenzo-nitrile, 2,5-dimethyl-anisole, 2,4-dimethylanisole, benzonitrile, 3,5-dimethyl-anisole, N,N-dimethylaniline, ethyl benzoate, 1-fluoro- 3,5-dimethoxy-benzene, 1-methylnaphthalene, 2-methylnaphthalene, N-methylpyrrolidinone, 3-fluorobenzo-trifluoride, benzotrifluoride, dioxane, trifluoromethoxy-benzene, 4-fluorobenzotrifluoride, 3-fluoropyridine, toluene, 2-fluoro-toluene, 2-fluorobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, pyridine, 4-fluorotoluene, 2,5-difluorotoluene, 1-chloro-2,4-difluorobenzene, 2-fluoropyridine, 3-chlorofluorobenzene, 1-chloro-2,5-difluorobenzene, 4-chlorofluorobenzene, chlorobenzene, o- dichloro-benzene, 1,2,4-dichlorobenzene, 2-chlorofluorobenzene, 1,8-diiodooctan, 1,8-octanedithiol, nitrobenzene, 1-chloronaphthalene, p-xylene, m-xylene, o-xylene or mixture of o-, m- and p- isomers. Relatively low polarity solvents are generally preferred. Examples of especially preferred solvents include, without limitation, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, 1,2,4-dichlorobenzene, anisole, 2,5-dimethylanisole, 2,4-dimethylanisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1-methylnaphthalene, 1,8-diiodooctane, 1,8-octanedithiol, nitrobenzene, tetralin, decalin, indane, methyl benzoate, ethyl benzoate, mesityleum and/or mixtures thereof.

[00246] The OPV device can be any type of OPV device known from the literature (see, for example, Waldauf et al., Appl. Phys. Lett., 2006, 89, 233517).

[00247] A first preferred OPV device according to the invention comprises the following layers (in sequence from bottom to top):

[00248] - optionally a substrate,

[00249] - a high working function electrode, preferably comprising a metal oxide, such as, for example, ITO, serving as an anode or a conduction grid

[00250] - an optional conduction polymer layer or orifice-transport layer, preferably comprising an organic polymer or polymer blend, for example, of PEDOT:PSS (poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) , or TBD (N,N'-diphenyl-N-N'-bis(3-methylphenyl)-1,1'biphenyl-4,4'-diamine) or NBD (N,N'-diphenyl-N-N' -bis(1-naphthyl-phenyl)-1,1'biphenyl-4,4'-diamine),

[00251] - a layer, also referred to as "photoactive layer", comprising a p-type organic semiconductor and an n-type that can exist, for example, as a p-type/n-type bilayer or as distinct p-type layers, or as mixture or semiconductor type pe type n, forming a BHJ,

[00252] - optionally a layer having electron transport properties and/or orifice blocking properties, for example comprising LiF or PFN,

[00253] - a low work function electrode, preferably comprising a metal such as, for example, aluminum, serving as a cathode,

[00254] where at least one of the electrodes, preferably the anode, is at least partially transparent to visible light, and

[00255] where the n-type semiconductor is a fullerene derivative of the present invention.

[00256] A second preferred OPV device according to the invention is an inverted OPV device and comprises the following layers (in sequence from bottom to top):

[00257] - optionally a substrate,

[00258] - a high working function metal or metal oxide electrode comprising, for example, ITO, serving as a cathode, or a conduction grid

[00259] - a layer having hole blocking properties and/or an electron-selective contact, preferably comprising a metal oxide such as TiOx or ZnOx and/or an organic layer or a polyamine such as PEI:DEG or PEIE.

[00260] - a photoactive layer comprising an organic semiconductor type p and an n type, situated between the electrodes, which can exist, for example, as a p-type/n-type bilayer or as distinct n-type p-type layers or as a mixed semiconductor or type pe type n, forming a BHJ,

[00261] - an optional conduction polymer layer or orifice transport layer, preferably comprising a small organic molecule and/or polymer and/or polymer mixture, for example, PEDOT:PSS or TBD or NBD,

[00262] - an electrode comprising a high-working function metal such as, for example, silver, serving as an anode,

[00263] where at least one of the electrodes, preferably the cathode, is at least partially transparent to visible light, and

[00264] where the n-type semiconductor is a fullerene derivative of the present invention.

[00265] In the OPV devices of the present invention the p-type and n-type semiconductor materials are preferably selected from materials such as polymer/fullerene systems as described above.

[00266] When the photoactive layer is deposited on the substrate, it forms a BHJ that separates into phases at the nanoscale level. For a discussion of nanoscale phase separation see Dennler et al., Proceedings of the IEEE, 2005, 93 (8), 1429 or Hoppe et al., Adv. Func. Mater, 2004, 14(10), 1005. An optional annealing step may then be necessary to optimize the mixture morphology and hence OPV device performance.

[00267] Another method to optimize device performance is to prepare formulations for the manufacture of OPV(BHJ) devices that can include additives with variable boiling points to promote phase separation in the correct manner. 1,8-octanediol, 1,8-diiodooctane, nitrobenzene, chloronaphthalene and other additives have been used to obtain high efficiency solar cells. Examples are disclosed in J. Peet et al., Nat. Mater., 2007, 6, 497 or Fréchet et al., J. Am. Chem. Soc., 2010, 132, 7595-7597.

[00268] [0186] As further illustrated in the non-limiting working examples, photovoltaic devices can be prepared which have a Power Conversion Efficiency (PCE) of, for example, at least 2.5% or at least 3.0% or at least 4.0% or at least 5.0%. While there is no particular upper limit on PCE, PCE can be, for example, less than 20% or less than 15% or less than 10%.

[00269] The fullerene derivatives, fullerene compositions and semiconductor layers of the present invention are also suitable for use as n-type semiconductor in other OE devices or device components, for example, in the semiconductor channel of an OFET device, or in the buffer layer , electron transport layer (ETL) or orifice blocking layer (HBL) of an OLED or OPV device.

[00270] In this way, the invention also provides an OFET comprising a gate electrode, an insulating layer (or gate insulator), a source electrode, a drainage electrode and an organic semiconductor channel connecting the source and drainage electrodes, wherein the organic semiconductor channel comprises a fullerene derivative of the present invention, a fullerene composition or an organic semiconductor layer according to the present invention as n-type semiconductor. Other features of OFET are well known to those skilled in the art.

[00271] OFETs where an OSC material is disposed as a thin film between a gate and a drain dielectric electrode and a source are generally known and are described, for example, in US 5,892,244, US 5,998,804, US 6,723 .394 and the references mentioned in the Background section. Due to advantages such as low production cost using the solubility properties of compounds according to the invention and thus the processability of large surfaces, preferred applications of these FETs are applications such as integrated circuit, TFT displays and security.

[00272] The gate, source and drain electrodes and the insulation and semiconductor layer in the OFET device can be arranged in any sequence, provided that the source and drain electrode are separated from the gate electrode by the insulation layer, the electrode The gate and the semiconductor layer both contact the insulating layer and the source electrode and the drain electrode both contact the semiconductor layer.

[00273] An OFET device according to the present invention preferably comprises:

[00274] - a source electrode,

[00275] - a drainage electrode,

[00276] - a door electrode,

[00277] - a semiconductor layer,

[00278] - one or more layers of door insulation,

[00279] - optionally a substrate.

[00280] wherein the semiconductor layer comprises a fullerene derivative of the present invention or a fullerene composition as described above and below.

[00281] The OFET device can be an upper port device or a lower port device. Suitable fabrication structures and methods of an OFET device are known to the person skilled in the art and are described in the literature, for example in US 2007/0102696 A1 .

The door insulation layer preferably comprises a fluoropolymer, such as, for example, commercially available Cytop 809M® or CYtop 107M® (from Asahi Glass). Preferably the door insulation layer is deposited, for example, by spin coating, scalpel, wire rod coating, spray or dip coating or other known methods, from a formulation comprising an insulating material and one or more solvents with one or more fluorine atoms (fluorosolvents), preferably a perfluorosolvent. A suitable perfluorosolvent is, for example, FC75® (available from Acros, catalog number 12380). Other suitable fluoropolymers and fluorosolvents are known in the prior art, such as, for example, the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont) or Fluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377). Especially preferred are organic dielectric materials having a low permittivity (or dielectric constant) of from 1.0 to 5.0, more preferably from 1.8 to 4.0 ("low k materials"), as disclosed, for example, in US 2007/0102696 A1 or US 7,095,044.

[00283] In security applications, OFETs and other devices with semiconductor materials in accordance with the present invention, such as transistors or diodes, can be used for RFID tags or security markers to authenticate and prevent counterfeiting of documents of value such as banknotes, credit cards or identities, national identity documents, licenses or any product with monetary value, such as stamps, tickets, shares, checks, etc.

[00284] Alternatively, the fullerene derivatives, fullerene compositions and semiconductor layers according to the invention can be used in OLEDs, for example, in the buffer, ETL or HBL layer of an OLED. The OLED device can be used, for example, as the active screen layer on a flat-tile monitor or as the backlight of a flat-panel monitor such as, for example, a liquid crystal display. Common OLEDs are obtained using multilayer structures. An emission layer is generally sandwiched between one or more electron transport and/or orifice transport layers. By applying an electrical voltage electrons and orifices as charge vehicles move towards the emission layer where their recombination leads to excitation and then luminescence of the luminophore units contained in the emission layer.

[00285] The fullerene derivatives, fullerene composition or semiconductor layer according to the present invention can be employed in one or more of ETL, HBL or buffer layer, especially their water-soluble derivatives (for example, with polar side groups or ionic) or ionically doped forms. Processing such layers, comprising a semiconductor material of the present invention, for use in OLEDs is generally known to a person skilled in the art, see, for example, Müller et al., Synth. Metals, 2000, 111-112, 31-34, Alcala, J. Appl. Phys., 2000, 88, 7124-7128, O'Malley et al., Adv. Energy Mater. 2012, 2, 82-86 and the literature mentioned therein.

[00286] According to another use, fullerene derivatives, fullerene compositions and materials according to the present invention, especially those showing photoluminescent properties, can be employed as light source materials, for example, in display devices, as described in EP 0 889 350 A1 or by Weder et al., Science, 1998, 279, 835-837.

[00287] A further aspect of the invention relates to both oxidized and reduced forms of a fullerene derivative according to the present invention. Either loss or gain of electrons results in the formation of a highly displaced ionic form, which is of high conductivity. This can occur when exposed to common dopants. Suitable dopants and methods of doping are known to those skilled in the art, for example from EP 0 528 662, US 5,198,153 or WO 96/21659.

[00288] The doping process typically entails treating the semiconductor material with an oxidizing or reducing agent in a redox reaction to form displaced ionic centers in the material, with the corresponding counterions derived from the applied dopants. Suitable doping methods comprise, for example, exposure to a doping vapor at atmospheric pressure or at reduced pressure, electrochemical doping in a solution containing a dopant, bringing a dopant into contact with the semiconductor material to be thermally molten, and ion implant of the dopant in the semiconductor material.

[00289] When electrons are used as vehicles, suitable dopants are, for example, halogens (eg I2, Cl2, Br2, ICl, ICl3, IBr and IF), Lewis acid (eg PF5, AsF5, SbF5, BF3 , BCl3, SbCl5, BBr3 and SO3), proton acids, organic acids or amino acids (eg HF, HCl, HNO3, H2SO4, HClO4, FSO3H and ClSO3H), transition metal compounds (eg FeCl3, FeOCl, Fe (ClO4)3, Fe(4-CH3C6H4SO3)3, TiCl4, ZrCl4, HfCl4, NbF5,NbCl5, TaCl5, MoF5, MoCl5, WF5, WCl6, UF6 and LnCl3 (where Ln is a lanthanide), anions (eg Cl -, Br-, I-, I3-, HSO4-, SO42-, NO3-, ClO4-, BF4-, PF6-, AsF6-, SbF6-, FeCl4-, Fe(CN)63-, and anions of various acids sulfonics, such as aryl-SO3-). When orifices are used as vehicles, examples of dopants are cations (eg, H+, Li+, Na+, K+, Rb+ and Cs+), alkali metals (eg, Li, Na, K , Rb, and Cs), alkaline earth metals (eg, Ca, Sr, and Ba), O2, XeOF4, (NO2+) (SbF6-), (NO2+) (SbCl6-), (NO2+) (BF4-) , AgClO4, H2IrCl6, La(NO3)3 . 6H2O, FSO2OOSO2F, Eu, acetylcholine, R4N+, (R is an alkyl group), R4P+ (R is an alkyl group), R6As+ (R is an alkyl group) and R3S+ (R is an alkyl group).

[00290] The conductive form of a fullerene derivative of the present invention can be used as an organic "metal" in applications including, but not limited to, charge injection layers and ITO planarizing layers in OLED applications, films for flat panel monitors and touch screens, antistatic films, printed conductive substrates, patterns or tracts in electronic applications such as printed circuit boards and capacitors.

[00291] According to another use, the fullerene derivatives and fullerene compositions according to the present invention can be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described, for example , in US 2003/0021913. The use of charge-carrying compounds in accordance with the present invention can increase the electrical conductivity of the alignment layer. When used in an LCD, this increased electrical conductivity can reduce adverse residual dc defects in the switchable LCD cell and suppress temporary image retention or, for example, in ferroelectric LCDs, reduce the residual charge produced by switching the spontaneous polarization charge of the Ferroelectric LCs. When used in an OLED device comprising a light-emitting material provided over the alignment layer, this increased electrical conductivity can increase the electrochemiluminescence of the light-emitting material. Fullerene derivatives, fullerene compositions and materials according to the present invention may also be combined with photoisomerizable compounds and/or chromophores for use in or as photoalignment layers as described in US 2003/0021913 A1.

[00292] According to another use of fullerene derivatives, fullerene compositions and materials according to the present invention, especially their water-soluble derivatives (e.g., with polar or ionic side groups) or ionically doped forms, may be employed as chemical sensors or materials for detecting and discriminating DNA sequences. Such uses are described, for example, in L. Chen, D.W. McBranch, H. Wang, R. Helgeson, F. Wudl and D.G. Whitten, Proc. Natl. Academic Sci. U.S.A., 1999, 96, 12287; D. Wang, X. Gong, P.S. Heeger, F. Rininsland, G.C. Bazan and A.J. Heeger, Proc. Natl. Academic Sci. U.S.A., 2002, 99, 49; N. DiCesare, M.R. Pinot, K.S. Schanze and J.R. Lakowicz, Langmuir, 2002, 18, 7785; D.T. McQuade, A.E. Pullen, T.M. Swager, Chem. Rev., 2000, 100, 2537.

[00293] [Unless the context clearly indicates otherwise, as used herein plural forms of terms herein shall be considered to include the singular form and vice versa.

[00294] Throughout the report and claims of this application, the words "comprise" and contain" and variations of the words, for example, "comprising" and "comprises", mean "including, but not limited to" and are not intended (and not) exclude other compounds.

[00295] It will be understood that variations on the above embodiments of the invention may be made while still falling within the scope of the invention. Each feature disclosed in the present application, unless otherwise specified, may be replaced by alternative features serving the same, equivalent or similar purpose. In this way, unless otherwise stated, each revealed feature is an example only of a generic series of equivalent or similar features.

[00296] All features disclosed in this application may be combined in any combination, except combinations where at least one of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and can be used in any combination. Likewise, features described in non-essential combinations can be used separately (not in combination).

[00297] Above and below, unless otherwise stated, percentages are percent by weight and temperatures are given in oC. The values of the dielectric constant ε ("allowance") refer to values obtained at 20°C and 1000 Hz.

[00298] The invention will now be described in more detail with reference to the following examples, which are illustrative only and do not limit the scope of the invention. A) Examples of CompoundExample 1Example 1.1 - 1,2-dihexylbenzene (1.2)

[00299] [0210] An oil bath was raised to 40°C. To a clean, dry, clean, 3-neck round bottom flask with stir bar was added 2.48 g (102.0 mmol, 24.305) g/mol, 2.5 eq.) of magnesium. The flask was fitted with a condenser, closed and purged three times with nitrogen and vacuum. Anhydrous ethyl ether (100 ml) was added via syringe and the mixture was stirred and brought to reflux. A trace amount of iodine was added under excess nitrogen pressure (the reaction turned colored and then clear again). To this mixture was added 14.32 ml (102.0 ml, 165.07 g/mol, 2.5 eq., 1.176 g/ml) of 1-bromo-hexane over 1 hour in drops using a syringe and pump. syringe. During the addition the reflux became more vigorous and was treated by adjusting the syringe pump speed. The mixture was stirred at reflux for a further 30 minutes after the addition was complete and then the reaction was allowed to cool. To a second 500 mL, dry, clean, 3-neck round bottom flask, a stir bar and 110.6 mg (0.204 mmol, 0.005 eq., 542.04 g/mol) of [1 catalyst] were added. 3-bis(diphenylphosphino)propane]dichloro-nickel(II). This second flask was also equipped with a condenser and purged three times with argon and vacuum. Anhydrous ethyl ether (50 mL) and 4.6 mL (40.8 mmol, 147.01 g/mol, 1 eq., 1.306 g/mL) of 1,2-dichlorobenzene (1.1) were both added via syringe and this second mixture was stirred and brought to reflux. The Grignard reagent prepared above was added dropwise using a syringe and syringe pump for 1 hour. Precipitation was observed to start and then stop during the addition of the unfiltered Grignard. After the addition, additional portions of the nickel catalyst were added under excess nitrogen pressure to restart and bring the reaction to completion. Including the 0.005 eq. original, a final total of 0.035 eq. of Nickel catalyst was added. Care was taken to control the rate of reflux. The reaction was removed from the hot bath during catalyst additions. A large amount of salt was observed to erupt around the time the reaction was almost complete and the stir speed was adjusted to handle the extra viscosity. The reaction was then allowed to stir at reflux for another two nights. After cooling, the reaction was poured into an ice bath and 10% HCl was added carefully to quench. The mixture was transferred to a separatory funnel, the ether layer was separated from the water layer, the water layer was washed twice with ether and the ether portions were combined. The ether portions were then washed with water, saturated sodium bicarbonate (Caution! Gas evolution!) and brine, dried over magnesium sulfate, filtered and the solvent removed by rotary evaporation. Chromatography on silica in hexane provided 8 g (79.5% yield) of product (1.2) as a clear oil after rigorous removal of solvent. The final product contained small amounts of hexylbenzene and 1-chloro-2-hexylbenzene via GC-MS. 1H NMR (500 MHz, CDCl3 (adjusted to 7.26 ppm)) δ 7.124 (m, 4H), 2.596 (t, J = 8.0 Hz, 4H), 1.571 (m, 4H), 1.385 (m, 4H) ), 1.323 (m, 8H), 0.897 (t, 6H). Example 1.2 - 1,2-bis(1-bromohexyl)benzene (1.3)

[00300] An oil bath was raised to 80°C. To a clean, dry 250 ml round bottom flask was added a stir bar, 3.03 g (17.04 mmol, 177.98 g/ mol, 2.1 eq.) of N-bromosuccinimide, 2 g (8.12 mmol, 2467.43 g/mol, 1 eq.) of the starting material (1.2) by weight using a dripper and 12.6 mg of benzoyl peroxide. The flask was fitted with a condenser, then capped and purged three times with nitrogen and vacuum. Anhydrous carbon tetrachloride (50 ml) was added by syringe and the reaction was dropped into the 80°C oil bath, allowed to stir at reflux overnight. Succinamide is seen to float, indicating that the reaction is complete. Carbon tetrachloride was rotary evaporated, hexane added, the mixture sonicated and the succinamide removed by filtration. The hexane was then removed via rotary evaporation to provide 2.9 g (88% yield) of desired product (1.3) as an oil and possible mixture of isomers. This material was used directly in the next reaction mixture without further purification or other manipulation. It is important to note that this species was observed to decompose rapidly to silica gel.Example 1.3 - Fullerene 1

An oil bath was brought to 130°C. To a clean, dry, 500 mL 3-necked round bottom flask containing a stir bar was added 1.334 g (1.85 mmol, 2 eq., 720.64 g/mol) of C60 fullerene, 0.6635 g (3.997 mmol, 4.32 eq., 166.00 g/mol) of potassium iodide and 3.977 g (15.05 mmol, 16.26 eq. , 264.32 g/mol) of [18]crown[6]. The round bottom was fitted with a condenser, sealed and purged three times with nitrogen and vacuum. Anhydrous toluene (~330 mL) was added via cannula and the mixture was allowed to reflux. 374 mg (0.925 mmol, 1 eq., 404.22 g/mol, 1.312 g/mL) of the dibromide (1.3) was then added via syringe in anhydrous toluene and the reaction was refluxed and stirred in the dark overnight. other. After cooling, the reaction mixture was washed with 5% sodium hydroxide solution and water (350 mL), dried over magnesium sulfate, filtered and toluene was removed by rotary evaporation. The crude material was purified using silica gel chromatography with decalin as the eluent, followed by preparative intermediate pressure liquid chromatography using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase. Fractions containing product were combined and solvent removed using rotary evaporation. The sample was left in an oven overnight at 70°C under reduced pressure to remove residual solvent. The product (Fulerene 1) was isolated (230 mg, 25.8%) as a brown crystalline solid. Purity was confirmed at 99.59% by analytical HPLC using a column with CosmosilBuckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase.1H NMR (500 MHz, toluene-d8 (methyl adjusted to 2.09 ppm)) δ 7.527 (AA' to AA'BB', 2H), 7.411 (BB' to AA'BB', 2H), aliphatic signals not assigned with certainty.Example 2Example 2.1 - Fullerene 2

[00302] An oil bath was brought to 130°C. To a clean, dry, dry, 500 mL 3-neck round bottom flask containing a stir bar was added 1 g (1.19 mmol, 1.5 eq., 840.75 g/mol) of C70 fullerene, 0.5686 g (3.43 mmol, 4.32 eq., 166.0 g/mol) of potassium iodide and 3.41 g (12.90 mmol, 16.26 eq., 264.32 g/mol) of [18]crown[6]. The round bottom was fitted with a condenser, sealed and purged three times with nitrogen and vacuum. Anhydrous toluene (~285 mL) was added via cannula and the mixture was allowed to reflux. 320.5 mg (0.793 mmol, 1 eq., 404.2 g/mol, 1.312 g/mL) of the dibromide (1.3) was added via syringe in anhydrous toluene and the reaction was refluxed and stirred in the dark overnight for one day. the other. After cooling, the reaction mixture was washed with 5% sodium hydroxide solution and water (350 mL), dried over magnesium sulfate, filtered and toluene was removed by rotary evaporation. The crude material was purified using silica gel chromatography with decalin as the eluent, followed by preparative intermediate pressure liquid chromatography using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase. Fractions containing product were combined and solvent removed using rotary evaporation. The sample was left in an oven overnight at 70°C under reduced pressure to remove residual solvent. The product (Fulerene 2) was isolated (300.3 mg, 34.9%) as a dark brown crystalline solid. Purity was confirmed at 99.61% for the mixture of isomers by analytical HPLC using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase.Example 3Example 3.1 - 1,2-dipentylbenzene (3.1)

[00303] An oil bath is raised to 40°C. To a 3-neck round bottom flask, 250 cm3, dry, clean, with stir bar, is added 1.24 g (51.0 mmol, 2, 50 eq.) of magnesium. The flask is equipped with a condenser, capped and purged three times with nitrogen and vacuum. Anhydrous diethyl ether (50 cm 3 ) is added via syringe and the mixture is stirred and brought to reflux. A trace amount of iodine is added under pressure in excess of nitrogen. To this mixture is added 6.33 cm3 (51.0 mmol, 2.5 eq.) of 1-bromopentane over 1 hour in drops using a syringe and syringe pump. During addition, the backflow has become more vigorous and is treated by adjusting the speed of the syringe pump. The mixture is stirred at reflux for a further 30 minutes after the addition is complete and then the reaction is allowed to cool. To a second round bottom 3-neck flask, 250 cm 3 , dry, clean, a stir bar and 443 mg (0.816 mmol, 0.0400 eq.) of [1,3-bis(diphenylphosphino)propane]dichloronickel are added (II). This second flask is also equipped with a condenser and purged three times with nitrogen and vacuum. Anhydrous diethyl ether (25 cm3 ) and 2.3 cm3 (20.4 mmol) of 1,2-dichlorobenzene (1.1) are both added via syringe and this second mixture is stirred and brought to reflux. The Grignard reagent prepared above is added dropwise without filtration using a syringe and syringe pump for 1 hour after the Grignard reagent is added, plus 443 mg (0.816 mmol, 0.0400 eq.) of [1,3-bis ( diphenylphosphino)propane]dichloronickel(II) are added under pressure in excess of nitrogen. The reaction is then allowed to stir at reflux for three nights. After cooling, the reaction is poured into an ice bath with stirring and 10% hydrochloric acid is carefully added to quench. The mixture is transferred to a separatory funnel, the diethyl ether layer is separated from the water layer and the water layer is washed twice with water, and the ether portions are combined. The ether portions are then washed with water, saturated sodium bicarbonate and brine, dried over magnesium sulfate, filtered and the solvent removed by rotary evaporation. Chromatography on silica in hexanes provided 2.15 g (48.2% yield) of the title product as a clear oil after rigorous removal of solvent. 1H NMR (500 MHz, CDCl3 (adjusted to 7.26 ppm)) δ 7128 (m, 4H), 2.600 (t, J = 8.0 Hz, 4H), 1.582 (m, 4H), 1.4-1 .3 (m, 8H), 0.912 (t, 6H). Example 3.2 - 1,2-bis(1-bromopentyl)benzene (3.2)

3.2 Fulereno 3[00304] An oil bath is increased to 80°C. To a dry, clean 100 cm3 round bottom flask is added a stir bar, 1.20 g (6.73 mmol, 2.10 eq. ) of N-bromosuccinimide, 0.700 g (3.21 mmol, 1.00 eq.) of starting material (3.1) by weight using a dropper and 5 mg of benzoyl peroxide. The flask is equipped with a condenser, then capped and purged three times with nitrogen and vacuum. Carbon tetrachloride (17.5 cm 3 ) is added via syringe and the reaction is dropped into the 80°C oil bath and allowed to stir at reflux overnight. Carbon tetrachloride is removed in vacuo, hexane is added, the mixture is sonicated and the succinamide removed by filtration. The hexane is then removed in vacuo to provide 1.21 g (quantitative) of desired product (3.2) as an oil and possible mixture of isomers. This material was used directly in the next reaction without further purification or other manipulation. Example 3.3 - Fullerene 3

3.2 Fullerene 3

[00305] An oil bath is brought to 130°C. To a clean, dry 2 dm3 round bottom flask containing a stir bar is added ~1.3 dm3 of toluene, 2.88 g (4 .00 mmol, 2.00 eq.) of C60 fullerene, 1.43 g (8.64 mmol, 4.32 eq.) of potassium iodide and 8.60 g (32.5 mmol, 16.3 eq. ) of [18]crown[6]. The round bottom is equipped with a condenser, sealed and purged three times with nitrogen and vacuum. The mixture is lowered into the oil bath and allowed to reach reflux. 752.4 mg (2.00 mmol, 1 eq., 376.18 g/mol) of 1,2-bis(1-bromopentyl)benzene (3.2) are then added via syringe in ~137 cm3 of toluene. The reaction is refluxed and stirred in the dark overnight. After cooling, the reaction mixture is washed twice with 250 cm3 of sodium hydroxide solution and twice with 250 cm3 of water, dried with magnesium sulfate, filtered and toluene is removed by rotary evaporation. The crude material is purified using silica gel chromatography with decalin as the eluent (twice in the same column) to remove C60, followed by preparative intermediate pressure liquid chromatography using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to pyrenylpropyl group) and toluene as the mobile phase. Fractions containing pure product are combined and solvent removed using rotary evaporation. The sample is left in an oven overnight at 70°C under reduced pressure to remove residual solvent. Fullerene 3 is isolated (376 mg, 20%) as a brown crystalline solid. Example 4Example 4.1 - 1,2-diheptylbenzene (4.1)1-bromoethane magnesium iodine

[00306] An oil bath is increased to 40°C. To a 3-neck round bottom flask, 250 cm3, dry, clean, with stir bar, 2.70 g (111 mmol, 2.50 eq) are added .) of magnesium. The flask is equipped with a condenser, capped and purged three times with nitrogen and vacuum. Anhydrous diethyl ether (125 cm3 ) is added via syringe and the mixture is stirred and brought to reflux. A trace amount of iodine is added under pressure in excess of nitrogen. To this mixture 17.5 cm3 (111 mmol, 2.50 eq.) of 1-bromoeptane is added over 1 hour in drops using a syringe and syringe pump. The mixture is stirred at reflux for a further 30 minutes after the addition is complete, and then the reaction is allowed to cool. To a second, dry, clean, 3-neck round bottom flask, 500 cm 3 , is added a stir bar and 1.20 g (2.21 mmol, 0.0500 eq.) of [1,3-bis(diphenylphosphine) ) propane] dichloronickel(II). This second flask is also equipped with a condenser and purged three times with nitrogen and vacuum. Anhydrous diethyl ether (62.5 cm3) and 1,2-dichlorobenzene (1.1) (5.00 cm3, 44.4 mmol, 1.00 eq.) are both added via syringe and this second mixture is stirred and brought up. for reflux. The Grignard reagent prepared above is added dropwise using a syringe and syringe pump over 45 minutes while concurrently filtering through a large PTFE filter. After the Grignard is added, an additional 600 mg (1.11 mmol, 0.0250 eq.) of [1,3-bis(diphenylphosphino)propane]dichloronickel(II) are added under excess nitrogen pressure. The reaction is allowed to stir at reflux overnight. After cooling, the reaction is poured into an ice bath with stirring and 10% hydrochloric acid (92 cm3, 2.5 eq.) is added carefully to cool. The mixture is transferred to a separatory funnel, the diether layer is separated from the water layer, the water layer is washed twice with diethyl ether and the organic fractions are combined. The organic fractions are then washed with water, saturated sodium bicarbonate and brine, dried over magnesium sulfate, filtered and the solvent removed in vacuo. Hexane is added and precipitation is observed. The precipitate is filtered through a small plug of silica which is then rinsed with plenty of hexane. The solvent filtrate is removed in vacuo to give 9.61 g of an almost colorless oil. The oil is then subjected to Kugelrohr distillation for ~30 minutes at 150°C and high vacuum to provide 4.8 g (39.3% yield) of product (4.1) as an almost colorless clear oil. 1H NMR (500 MHz, CDCl3 (adjusted to 7.26 ppm)) δ 7.147 (m, 4H), 2.620 (t, J = 8.0 Hz, 4H), 1.55 - 1.65 (m, 4H) , 1.45-1.25 (m, 16H), 0.915 (t, 6H). Example 4.2 - 1,2-bis(1-bromoeptyl)benzene (4.2)

[00307] [0218] An oil bath is raised to 80°C. To a 100 cm3 round bottom flask, dry, clean, a stir bar, 4.28 g (24.1 mmol, 2.20) is added eq.) of N-bromosuccinimide, 3.00 g (10.9 mmol, 1.00 eq.) of 1,2-diepylbenzene (4.1) and 17.1 mg of benzoyl peroxide. The flask is equipped with a condenser, then capped and purged three times with nitrogen and vacuum. Carbon tetrachloride (60 cm 3 ) is added via syringe and the reaction is dropped into the 80°C oil bath and allowed to stir at reflux overnight. Carbon tetrachloride is removed in vacuo, hexane is added, the mixture is sonicated and the succinimide is removed by filtration. The hexane is then removed in vacuo to give 4.75 g (quantitative) of the title product (4.2) as an oil and possible mixture of isomers. This material is used directly in the next reaction without further purification or other manipulation. Example 4.3 - Fullerene 4

[00308] An oil bath is brought to 130°C. To a 2 dm3 dry, clean two-necked round bottom flask containing a stir bar is added 11.8 g (16.4 mmol, 1 .50 eq.) of C60 fullerene, 7.84 g (47.2 mmol, 4.32 eq.) of potassium iodide, 47.0 g (177.74 mmol, 16.3 eq.) of [18] corona[6] and 1.5 dm3 of toluene. The round bottom is equipped with a condenser, sealed and purged three times with nitrogen and vacuum. The mixture is lowered into the oil bath and allowed to reach reflux. 4.73 g (10.9 mmol, 1.00 eq.) of 1,2-bis(1-bromoeptyl)benzene dibromide (4.2) are then added dropwise using a syringe and syringe pump in ~40 cm3 of toluene for 3 hours. The reaction is refluxed and stirred in the dark overnight after decreasing the oil bath temperature to 125 °C. After cooling, the reaction mixture is washed twice with 840 cm3 of 5% sodium hydroxide solution. After washings, the entire solution is filtered to provide 6.44 g of dry, almost pure C60. The filtrate is then washed twice with 840 cm3 of water, dried with magnesium sulphate, filtered and toluene removed in vacuo. The crude material is purified using silica gel chromatography with decalin as the eluent to remove C60, followed by preparative intermediate pressure liquid chromatography using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase. Fractions containing the high purity product are collected and combined. Most of the toluene is removed under vacuum. The bulk of the fullerene adduct has precipitated and is filtered to further improve purity. Samples are left in an oven overnight at 70°C under reduced pressure to remove residual solvent. Fullerene 4 was isolated in two fractions (968.6 mg and 584.5 mg, 14.3% total yield) as a brown crystalline solid. Purity is confirmed at 99.78% and 99.41%, respectively, by analytical HPLC using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase. 5Example 5.1 - 1,2-dioctylbenzene (5.1

[00309] An oil bath is increased to 40°C. To a 3-neck round bottom flask, 250 cm3, dry, clean, with stir bar, 2.70 g (111 mmol, 2.50 eq) are added .) of magnesium. The flask is equipped with a condenser, capped and purged three times with nitrogen and vacuum. Anhydrous diethyl ether (40 cm 3 ) is added via syringe and the mixture is stirred and brought to reflux. A trace amount of iodine is added under pressure in excess of nitrogen. To this mixture 19.2 cm3 (111 mmol, 2.50 eq.) of 1-bromooctane is added over 1 hour in drops using a syringe and syringe pump. The mixture is stirred at reflux for a further 30 minutes after the addition is complete, and then the reaction is allowed to cool. To a second, dry, clean, 3-neck round bottom flask, 500 cm 3 , is added a stir bar and 1.20 g (2.21 mmol, 0.0500 eq.) of [1,3-bis(diphenylphosphine) )propane]dichloronickel(II). This second flask is also equipped with a condenser and purged three times with nitrogen and vacuum. Anhydrous diethyl ether (148 cm3) and 1,2-dichlorobenzene (1.1) (5.00 cm3, 44.4 mmol, 1.00 eq.) are both added via syringe and this second mixture is stirred and brought to reflux . The Grignard reagent prepared above is added dropwise using a syringe and syringe pump over 45 minutes while concurrently filtering through a large PTFE filter. The reaction is allowed to stir at reflux for four. After cooling, the reaction is poured into an ice bath with stirring and 10% hydrochloric acid (92 cm3, 2.5 eq.) is added carefully to quench. The mixture is transferred to a separatory funnel, the diethyl ether layer is separated from the water layer, the water layer is washed twice with diethyl ether and the organic fractions are combined. The organic fractions are then washed with water, saturated sodium bicarbonate and brine, dried over magnesium sulfate, filtered and the solvent removed in vacuo. Hexane (250 cm3) is added and a precipitation is observed. The precipitate is filtered through a small plug of silica which is then rinsed with plenty of hexane. The solvent filtrate is removed in vacuo and the resulting oil is then subjected to Kugelrohr distillation for ~30 minutes at 150°C and high vacuum to provide 5.53 g (41.1% yield) of the title product as an oil. almost colorless transparent.Example 5.2 - 1,2-bis(1-bromooctyl)benzene (5.2)

5.2 Fulereno 5An oil bath is increased to 80°C. To a dry, clean 100 cm3 round bottom flask is added a stir bar, 1.37 g (7.67 mmol, 2.30 eq. ) of N-bromosuccinimide, 1.01 g (3.34 mmol, 1.00 eq.) of 1,2-dioctylbenzene (5.1) and 5.7 mg of benzoyl peroxide. The flask is equipped with a condenser, then capped and purged three times with nitrogen and vacuum. Carbon tetrachloride (20 cm 3 ) is added via syringe and the reaction is dropped into the 80°C oil bath and allowed to stir at reflux overnight. Carbon tetrachloride undergoes rotary evaporation, hexane is added, the mixture is sonicated and the succinamide removed by filtration. The hexane is then removed via rotary evaporation to provide 1.59 g (quantitative) of title product as an oil and possible mixture of isomers. This material is used directly in the next reaction without further purification or other manipulation. Example 5.3 - Fullerene 5

5.2 Fullerene 5

[00311] An oil bath is brought to 130°C. To a clean, dry, two-necked round bottom flask containing a stir bar was added 3.49 g (5.02 mmol, 1, 45 eq.) of C60 fullerene, 2.40 g (14.45 mmol, 4.32 eq., 166.00 g/mol) of potassium iodide, 14.38 g (54.40 mmol, 16.26 eq.) .) of [18]crown[6] and 1.5 dm3 of toluene. The round bottom is equipped with a condenser, sealed and purged three times with nitrogen and vacuum. The mixture is lowered into the oil bath and allowed to reach reflux. 1,2-Bis(1-bromooctyl)benzene (5.2) (1.54 g, 3.35 mmol, 1.00 eq.) of the dibromide is then added via syringe in one portion into 50 cm3 of reagent grade toluene. The reaction is refluxed and stirred in the dark overnight after decreasing the oil bath temperature to 125 °C. After cooling, the reaction mixture is washed twice with 250 cm3 of 5% sodium hydroxide solution. After washings, the entire solution is filtered to provide 454 mg of dry, almost pure C60. The filtrate is then washed twice with 250 cm3 of water, dried with magnesium sulphate, filtered and toluene removed by rotary evaporation. Purification is performed completely by preparative intermediate pressure liquid chromatography using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase. Fractions containing high purity product are collected and combined, then toluene is removed using rotary evaporation and the samples are left in an oven overnight at 70°C under reduced pressure to remove residual solvent. Fullerene 5 is isolated (580 mg, 17.0%) as a brown crystalline solid. Purity is confirmed at 99.76% by analytical HPLC using a column with Cosmosil Buckyprep material as the stationary phase (from Nacalai Tesque; silica bonded to the pyrenylpropyl group) and toluene as the mobile phase.B) Working ExamplesExample B1Organic photovoltaic device from volume heterojunction (OPV) of Fullerene 1 and Fullerene 2

[00312] Organic Photovoltaic Devices (OPV) are fabricated on pre-patterned ITO glass substrates (13Q/Wed.) purchased from LUMEC Corporation. Substrates are cleaned using common solvents (acetone, iso-propanol, deionized water) in an ultrasonic bath. A conducting polymer poly(ethylene dioxythiophene) doped with poly(styrene sulfonic acid) [Clevios VPAI 4083 (H.C. Starck)] is mixed in a 1:1 ratio with deionized water. This solution is filtered using a 0.45 µm filter before spin coating to obtain a thickness of 20 nm. Substrates are exposed to ozone prior to the spin coating process to ensure good wetting properties. The films are then annealed at 140°C for 30 minutes in a nitrogen atmosphere where they are held for the remainder of the process. Active material solutions (ie, polymer + fullerene) are prepared to fully dissolve the solutes. Thin films are either spin coated or blade coated in a nitrogen atmosphere to obtain active layer thicknesses between 50 and 500 nm as measured using a profilometer. A short drying period follows to ensure removal of any residual solvent.

[00313] Typically, blade-coated films are dried at 70°C for 2 minutes on a hot plate. For the last step of device fabrication, Ca (30 nm) / Al (100 nm) cathodes are thermally evaporated through a shadow mask to define the cells. Current-voltage characteristics are measured using a Keithley 2400 SMU while the solar cells are illuminated by a Newport Solar Simulator at 100 mW.cm-2 of white light. The solar simulator is equipped with AM1.5G filters. Illumination intensity is calibrated using a Si photodiode. All preparation and characterization of the device is done in a dry nitrogen atmosphere.

em que FF é definido como

[00314] Energy conversion efficiency is calculated using the expression that follows

where FF is defined as

[00315] OPV devices are prepared where the photoactive layer contains a mixture of a polymer 1 having the structure below and either oQDM-C60 or Fullerene 1 or Fullerene 2 of Example 1 or 2, respectively, which is coated with a solution of o- dichlorobenzene at a total solid concentration as shown in Table 1 below.

[00316] the QDM-C60 and its preparation are disclosed, for example, in Angewandte Chemie 1993, 105, 95-7.

Polymer 1

[00317] Polymer 1 and its preparation are disclosed in WO2011/131280.

Polymer 2

[00318] Polymer 2 and its preparation are disclosed in WO2013/135339.

Polymer 3

[00319] Polymer 3 and its preparation are disclosed in US 8455606 B2.Table 1. Photovoltaic cell characteristics

[00320] It can be seen that QDM-C60, which has lower solubility in common organic solvents, prohibits the formation of the proper morphology to obtain good performance in an OPV device, compared to fullerene C60 Fullerene 1, Fullerene 3, Fullerene 4 and Fullerene 5 according to the invention, which show significantly better performance. Example 3: Solubility Examples

[00321] Since controlling and increasing the solubility of fullerene derivatives used as n-phase material is an important aspect in many embodiments of the present invention, the solubility of Fullerene 1 and Fullerene 2 was determined at room temperature (about 22° C) in o-dichlorobenzene, compared to that of oQDM-C60. O-dichlorobenzene solvent is a common solvent for the deposition of active layers of OPV devices and is also used in the working examples here.

[00322] For this purpose, the procedure that follows for determining solubilities was used.

[00323] As the determination of concentration is based on the absorbance at 360 nm, a calibration curve is established first. Solutions of Fullerene 1, Fullerene 2 and oQDM-C60 in o-dichlorobenzene at concentrations of 0.1 mg/cm3 are prepared. By diluting the fractions of the solutions further, additional solutions at concentrations of 0.02 and 0.004 g/cm3 are obtained, respectively. UV-vis spectra between 300 and 1100 nm were measured and the absorbances at 360 nm were recorded. Absorbance vs. concentration was plotted for Fullerene 1 and Fullerene 2, respectively. Linear slope lines intersecting at (0.0) were added and the declines, to be used as response factors, recorded.

[00324] In order to assess the solubilities, concentrated solutions, saturation targets, of Fullerenes 1 to 5 and, for comparison, oQDM-C60 were prepared. In more detail: 57 mg of Fullerene 1, 85 mg of Fullerene 2, 82.9 mg of Fullerene 3, 78.3 mg of Fullerene 4, 157 mg of Fullerene 5 and 46 mg of oQDM-C60 were added to 1 cm3 of o- dichlorobenzene and stirred overnight with a magnetic stir bar. The solution was filtered through a 0.2 μm syringe filter and diluted with o-dichlorobenzene in order to obtain adequate concentrations for the UV-vis spectrometer. UV-vis spectra of the resulting solutions are measured and absorbances at 360 nm recorded.

[00325] Using the calibration curves described above and taking into account the dilution factors, the following solubilities in o-dichlorobenzene at room temperature were obtained: oQDM-C60: 5.8 mg/cm3Fulerene 1: 23 mg/cm3Fulerene 2 : > 85 mg/cm3 Fullerene 3: 9.3 mg/cm3 Fullerene 4: 45 mg/cm3 Fullerene 5: 20 mg/cm3

[00326] The value for Fullerene 2 is a minimum value since all material initially added has dissolved and the solution may not have been saturated. Finally, it can be concluded that functionalization schemes as described herein allow for an unexpectedly sharp increase in solubilities in a solvent pertinent to preparing OPV devices and other solvents and devices.

Claims (30)

1. Compound, having Formula I

whereCn is a fullerene composed of n carbon atoms, optionally with one or more atoms trapped inside, Adduct is a secondary adduct, or a combination of secondary adducts, attached to the fullerene Cn,m is the number of secondary adducts attached to the fullerene Cn , and is 0, an integer > 1 or a non-integer > 0,o is an integer > 1.R1 to R8 are independently of one another H, an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy group, all of which are straight-chain or branched, have from 2 to 20 C atoms and are optionally fluorinated, said compound being characterized by the fact that, in Formula I, at least one of R5 and R7 is different from H, and at least one of R6 and R8 is different from H. 2. Compound according to claim 1, characterized by the fact that one or more of R1, R2, R3, R4, R5, R6, R7 and R8 represent H. 3. Compound according to claim 1 or 2, characterized in that R5 and R6 are different from H and R7 and R8 mean H or R7 and R8 are different from H and R5 and R6 mean H. 4. Compound according to any one of claims 1 to 3, characterized in that n is 60, 70, 76, 78, 82, 84, 90, 94 or 96. 5. Compound, according to claim 4, characterized by the fact that n is 60. 6. Compound, according to claim 4, characterized by the fact that n is 70. 7. Compound according to any one of claims 1 to 6, characterized in that m is 0, 1, 2 or 3. 8. Compound according to claim 7, characterized by the fact that m is 1, 2 or 3. 9. Compound, according to claim 7, characterized by the fact that m is 0. A compound according to any one of claims 1 to 8, characterized in that the "Adduct" in Formula I is selected from the Formulas that follow

in which RS1, RS2, RS3, RS4 and RS5 independently of one another mean H, halogen or CN, either have one of the meanings of R1 as given in any one of claims 1 to 6 or have one of the meanings of ArS1 as given below, ArS1 and ArS2 are independently of one another an aryl or heteroaryl group having 5 to 20, preferably 5 to 15, ring atoms, which is mono- or polycyclic, and which is substituted by one or more identical or different RS substituents, where RS means halogen, preferably F, or a straight, branched or cyclic alkyl moiety having 1 to 30, preferably 4 to 20, more preferably 5 to 15, C atoms, one or more CH2 groups being optionally substituted by -O -, -S-, -C(O)-, -C(S)-, -C(O)-O-, -OC(O)-, -S(O)2-, -NR0-, -SiR0R00 -, -CF2-, where R0 and R00 denote H or an optionally substituted carboxyl or hydrocarbyl group having 1 to 40 carbon atoms. 11. Compound according to any one of claims 1 to 10, characterized in that it is selected from the subFormula that follows

in which Cn, "Adduct", m, R5 and R6 are as defined in any one of claims 1 to 6, with R5 and R6 being other than H. 12. Compound according to any one of claims 1 to 11, characterized in that it is selected from the following sub-formulas:

in which R5 and R6 independently of one another stand for straight or branched chain alkyl having 1 to 20 carbon atoms. 13. Use of the composite, as defined in any one of claims 1 to 12, characterized in that it is an electron acceptor or n-type semiconductor in a semiconductor material, electronic device or component of an organic electronic device. 14. Composition, characterized in that it comprises a compound as defined in any one of claims 1 to 12. 15. Composition according to claim 14, characterized in that it comprises one or more compounds, as defined in any one of claims 1 to 12, as an electron acceptor or n-type semiconductor component, and further comprising one or more compounds semiconductors that exhibit electron donor or p-type properties. 16. Composition according to claim 14 or 15, characterized in that it comprises one or more compounds as defined in any one of claims 1 to 12, and one or more p-type organic semiconductor compounds selected from conjugated organic polymers. 17. Composition according to any one of claims 14 to 16, characterized in that it comprises one or more compounds as defined in any one of claims 1 to 12, and one or more compounds that are selected from compounds having one or more than a property of semiconduction, charge transport, orifice transport, electron transport, orifice blocking, electron blocking, electrical conduction, photoconduction, and light emission. 18. Use of the compound as defined in any one of claims 1 to 12, or of the composition as defined in any one of claims 14 to 17, characterized in that it is a semiconductor, charge-carrying, electrically conductive, photoconductive material , thermoelectric or light-emitting material, or in an optical, electro-optic, electronic, electroluminescent or photoluminescent device or in a component such as a device or in an assembly comprising such device or component. 19. Semiconductor, charge-carrying, electrically conductive, photoconductive or light-emitting material, characterized in that it comprises the compound as defined in any one of claims 1 to 12, or the composition as defined in any one of claims 14 to 17. 20. Formulation, characterized in that it comprises one or more compounds, as defined in any one of claims 1 to 12, or the composition, as defined in any one of claims 14 to 17, and further comprising one or more organic solvents. 21. Optical, electro-optical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising the same, characterized in that it is prepared using the formulation as defined in claim 20. 22. Optical, electro-optic, electronic, electroluminescent or photoluminescent device, or a component of such a device, or an assembly comprising such a device, characterized in that it comprises the compound as defined in any one of claims 1 to 12, or the composition as defined in any one of claims 14 to 17 or the material as defined in claim 19. 23. Optical, electro-optic, electronic, electroluminescent or photoluminescent device according to claim 22, characterized in that it is selected from organic field effect transistors (OFET), organic thin-film transistors (OTFT) , organic light emitting diodes (OLEDs), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPDs), organic solar cells, thermoelectric device, laser diodes, Schottky diodes, photoconductors and photodetectors. 24. Optical, electro-optic, electronic, electroluminescent or photoluminescent device, or a component of such a device, or an assembly comprising such a device, according to claim 22, characterized in that the component of an optical device, electro -optical, electronic, electrochemiluminescent or photoluminescent is selected from charge injection layers, charge transport layers, interlayers, planarization layers, unsightly films, polymer electrolyte (PEM) membranes, conductive substrates and conduction patterns. 25. Optical, electro-optical, electronic, electroluminescent or photoluminescent device, or a component of such a device, or an assembly comprising such a device, according to claim 22, characterized in that the assembly is selected from integrated circuits (IC), radio frequency identification (RFID) markers or safety markers or safety devices containing the same, flat panel monitors or back lights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips. 26. Device according to claim 23, characterized in that it is a volume heterojunction OPV device (BHJ) or an inverted BHJ OPV device. 27. Bulky heterojunction, characterized by the fact that it comprises, or is being formed from, the composition, as defined in claim 26. 28. Method for manufacturing a compound of Formula I, as defined in any one of claims 1 to 12, characterized in that it comprises: reacting in one or more steps of a P-1 precursor represented by P-1,

in which R1 to R8 are as defined above and below, with at least one halogenating reagent to form a halogenated intermediate represented by P-2,

in which Hal means a halogen atom, and R1 to R8 are as defined above and below, andReacting intermediate P-2 in one or more steps with a fullerene compound represented by F-1 or F-2:

and, optionally, with a secondary adduct compound to form the Formula 1 compound. 29. Method according to claim 28, characterized in that intermediate compound P-2 is directly reacted without purification with the fullerene compound. 30. Method according to claim 28, characterized in that the intermediate compound P-2 is not contacted with untreated silica before being reacted with the fullerene compound.